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[0001] This application is a continuation-in-part of U.S. patent application Ser. No. 13/414,348 filed Mar. 7, 2012, which claimed the benefit of U.S. Provisional Application Ser. No. 61/450,185 filed Mar. 8, 2011, the benefit of which is claimed herein.
BACKGROUND OF THE INVENTION
[0002] Intermodal security is a major concern for all businesses that need to ship material goods via truck, rail and sea.
[0003] According to a recent report released by Federal Bureau of Investigation (FBI), industry experts estimate all cargo theft adds up to $30 billion each year. Besides thieves who break into random cargo containers, there have been instances where the driver responsible for the cargo is directly involved in the robbery. The FBI has also identified this and has attributed an offense code to ‘driver involved cargo theft’ in its Uniform Crime Report (UCR).
[0004] Locking devices and technologies currently available in the market limit themselves to physically locking the containers. Most of these products are one-time use products or require a physical key or combination for operation. The biggest disadvantage in this case is the lack of accountability in the event of theft. These devices offer no assistance in determining when and where the intrusion might have occurred.
[0005] A single-use lock requires additional cutting tools. Also, if the container needs to be opened at the request of law enforcement officials, it requires that the bolt be cut and a new bolt be installed. All of the cut bolts are either wasted or are recycled, which involves additional handling and shipping expenses.
[0006] In case of locking devices with a physical key or combination, there is a no record of when the lock has been operated. This situation can be used to the advantage of drivers, who often control the combination or key, with criminal intent who can tamper with the goods on board. Other reusable locks available come with a recurring expense of bolt-seal for each use.
[0007] Another aspect of cargo security is financial accountability in the event of theft. Cargo containers delivering goods usually see multiple modes of transportation including sea, train and road. When cargo theft occurs on such a complex route involving multiple individuals and shipping companies and if no proof exists as to when the theft occurred, it becomes extremely difficult for the insurance companies to determine financial responsibility.
[0008] Besides cargo theft, containers have also been targeted to smuggle illegal goods and people. US Customs and Border Protection (CBP) uses expensive technologies like X-ray, to deter these illegal activities. A security mechanism, which provides an electronic manifest of goods on board, an electronic log detailing the date and time when the container was accessed, and tamper sensors to provide a high level of confidence that the container was not compromised in transit is needed as an inexpensive and time-saving screening option for low-risk cargo.
[0009] The intermodal industry needs an affordable security solution which includes locking, event logging, tamper monitoring and optional GPS tracking.
SUMMARY OF THE INVENTION
[0010] The present invention is a re-usable, electro-mechanical, event-logging lock for cargo containers or similar enclosed spaces such as storage units. The robust locking mechanism includes a dual ratcheting cam, which firmly secures doors of a container or other enclosure. The lock continuously monitors lock status and detects tampering. The lock logs all operation and tampering events with a date and time stamp. The device is rugged, simple to operate, resistant to tampering, and will endure shock, rough handling and extreme weather conditions.
[0011] To unlock the device, the user obtains a temporary access code and unlocks the device, either by a wireless interface or by a physically connected interface such as, for example, a key pad. The device incorporates a rolling access code algorithm that changes the access code based upon a pre-defined and customer selected time period during which the code is valid. Once the validity period expires the user must obtain a new access code from a secure access code source to unlock the device. When access is desired, the user contacts a remote secure access code source, which provides the access code for the associated lock and time period. No form communication, wireless or otherwise, from the device to the access code source is required.
DESCRIPTION OF THE DRAWINGS
[0012] FIG. 1 is a front isometric view of a preferred embodiment
[0013] FIG. 2 is a front isometric view of another embodiment showing keypad
[0014] FIG. 3 is a rear isometric view of a preferred embodiment
[0015] FIG. 4 is a top view of a locking mechanism
[0016] FIG. 5 is a front view of the locking mechanism according to FIG. 4 .
[0017] FIG. 6 is a front isometric view of a preferred embodiment installed on an ISO container's keeper bars.
[0018] FIG. 7 is a front isometric view of a cover assembly of a preferred embodiment.
[0019] FIG. 8 is a rear view of the cover assembly of FIG. 7 .
[0020] FIG. 9 is the section A-A view of the cover assembly of FIG. 8 .
[0021] FIG. 10 is a system block diagram view of a circuit card assembly (CCA) schematic for an embodiment of the invention.
[0022] FIG. 11 shows a track security feature wherein an embodiment of the device transmits its geographic location using a wireless transmitter.
[0023] FIG. 12 shows a front view of an embodiment of the locking mechanism in the locked state.
[0024] FIG. 13 shows a rear view of the locking mechanism of FIG. 12 when locked.
[0025] FIG. 14 shows a front view of an embodiment of the locking mechanism of FIG. 12 in the unlocked state.
[0026] FIG. 15 shows a rear view of the locking mechanism of FIG. 12 in the unlocked state.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
[0027] A preferred embodiment provides a secure locking mechanism which can be used with shipping containers, including ISO styled cargo containers. Cargo container doors typically have vertical keeper bars, which are generally parallel bars, permanently attached to the doors of the container to secure the doors in the closed position during transit or storage. In a preferred embodiment, the device is constructed and arranged to be installed on the keeper bars. Once the embodiment is properly installed on keeper bars and locked, access to the container is prohibited. An alternate embodiment may be permanently installed on the interior of the container, such as the doors, or similar enclosure.
[0028] FIG. 1 shows a preferred embodiment of the invention when fully assembled. Front cover assembly 2 , back plate assembly 4 , and locking bar assembly 6 are the three major sub-assemblies involved. The locking bar 6 , which may be a J-shaped bar, or referred to as a J-bar, is inserted by slidable engagement with the lock, and retained in the lock that is present within the back plate assembly. A J-Bar assist handle 7 may be attached to the J-Bar to ease J-Bar operation. User interface 8 is present on the housing. The back plate of this embodiment has a U shaped member 10 , or U-bar, that is opposite the J-bar.
[0029] FIG. 2 shows an alternate embodiment of the invention that includes all of the elements of the embodiment of FIG. 1 . This embodiment further includes a keypad user interface 12 which may be used to enter an access code to unlock the device.
[0030] FIG. 3 shows a rear isometric view of an embodiment of the invention when fully assembled. The U-bar 10 , which may be formed as an extension of the back plate 4 , is installed on one keeper bar of the container. The sliding J-bar 6 is installed on the other keeper bar. The J-bar may be positioned as required to ensure a snug fit between the device and the keeper bars; FIG. 6 .
[0031] FIG. 4 shows a top view of an embodiment of the device with the front cover assembly removed. Mounting clamp 14 may be used with the U-bar 10 to secure the device on keeper bar while allowing the device to be rotated clear when opening the container. This construct inhibits the device from accidentally falling, thereby promoting safe use of the device. Once the embodiment is unlocked, the J-bar may be slidably extended, and the device may be rotated around the U-bar axis. Unencumbered access to the container is now available. This mounting clamp configuration eliminates the need to completely uninstall the embodiment from the container to gain access; thereby reducing cycle time while improving operational safety.
[0032] FIG. 5 shows a front view of an embodiment of the back plate assembly 4 in the locked state with the front cover assembly 2 removed. The locking mechanism of this embodiment uses two locking levers 18 , 20 that engage the valleys of the teeth 16 of the sliding J-bar 6 , preventing removal of the J-bar until the levers are disengaged by the operator. The locking mechanism operates on a cam principle, where the peaks and valleys of the teeth 16 act as a cam and the locking levers act as cam followers. The locking levers are held in a default locked position with the J-bar teeth fully engaged by a contraction spring 22 . The teeth of the J-bar preferably incorporate a slight inward angle, with edges 24 not being entirely vertical, as shown in the orientation of FIG. 5 . A linear opening (pulling) force applied to the J-bar results in the locking levers being pulled inwards by edges 24 toward the J-bar; thus ensuring the lock remains secure. Using the same cam principle while in the unlocked state, the locking levers are opened by the J-bar edges 36 as closing (pushing) force is applied to move the J-bar in the locking direction, but the levers will latch close when force is applied to pull the J-bar in the opposite direction. This allows the operator to install the J-bar easily with a ratcheting operation, but prevents movement of the J-bar in the opposite direction.
[0033] FIGS. 12 and 13 show further detail of the locking mechanism of a preferred embodiment in the locked state. In the locked state the J-bar is held firmly in position by the locking levers and cannot be opened (pulled) or closed (pushed). An important aspect of the locking mechanism is preventing rotation of the locking levers while in the locked state. In one embodiment, this is accomplished by a locking and unlocking actuator that comprises an electric double position linear solenoid 38 . Back plate assembly 4 comprises locking levers 18 , 20 that are held in position by the normally extended piston of the solenoid 38 , which inhibits movement (rotation) of the locking levers that are urged toward each other by contraction spring 22 . The solenoid piston, when extended, is physically positioned between the locking levers 18 , 20 , which prevents the release cam 30 from opening the locking levers to allow insertion or removal of the J-bar. Furthermore, the solenoid piston also prevents movement of the locking levers caused by external tampering, such as shock impacts of a sledge hammer. Only when the solenoid piston is retracted can the release button be depressed to actuate the release cam and allow the removal of the J-bar.
[0034] In one embodiment, a magnet 39 is installed on the edge of the solenoid piston as shown in FIG. 4 . A Hall Effect sensor 42 may be used to continuously monitor the magnetic field of the magnet. The solenoid piston position may be thereby monitored and the state of the lock determined.
[0035] FIG. 8 shows a rear view of the cover assembly and FIG. 9 shows a section view of FIG. 8 . Using the cam follower principle, a release cam 30 is employed in this embodiment to rotate the locking levers and allow the opening (pulling) of the J-bar. This second cam is attached to a release actuator, which may be a depressible button 32 , positioned on, for example, the left side of the cover assembly 2 . The release button is pressed and displaced, which actuates release cam 30 , rotating the locking levers, and allowing the operator to extend the J-bar. The release button and subsequently the release cam return to their original position with the help of expansion spring 34 . The release button mechanism is recessed in the cover assembly 2 and enclosed in a protective shroud 35 to inhibit damage from tampering. In an embodiment, the button 32 can spin in any direction without affecting the locking mechanism, so as to further inhibit damage from tampering.
[0036] FIG. 14 shows the device in the unlocked state with the solenoid piston retracted into the solenoid 38 . The releasing cam 40 is shown in the actuated position by the release button 32 between the locking levers 18 , 20 thereby rotating the locking levers away from the teeth of the sliding J-bar and disengaging them from the teeth. When the locking levers are disengaged from the teeth, the sliding J-bar may be extended (pulled) from the housing; the device is unlocked. FIG. 15 demonstrates the interaction between the locking levers 18 , 20 and the sliding J-bar 6 during the J-bar retraction (removal) step. With the locking mechanism in the unlocked state and cam 40 in the retracted (rest) position, the negative angle 36 on the sliding J-bar 6 tooth rotates the locking levers and permits insertion (push) of the J-bar with a ratcheting action.
[0037] FIG. 7 shows the front cover assembly of an embodiment having a Human Machine Interface (HMI) 44 . In the embodiment shown, the HMI has one button 62 and three Light Emitting Diodes (LED) 64 . The status LEDs on the HMI show the condition of the lock. For example, each LED may be assigned to one of the following: wireless (such as Bluetooth) connection status, battery status and lock state of the embodiment. More or fewer LEDs may be used to provide visual indications of various conditions of the lock. The button 62 may be used to wake the device from a low power (sleep) state; a single push wakes the microcontroller which then activates the wireless interface and illuminates the status LEDs accordingly. Pushing and holding button 62 for more than two seconds may cause the device to change from the unlocked state to the locked state; the lock status LED changing color accordingly.
[0038] FIG. 8 shows a rear view of the cover housing for a Circuit Card Assembly (CCA) 46 that may be used in a preferred embodiment. FIG. 10 shows a block diagram view of a preferred CCA schematic. The CCA in this embodiment has a microcontroller 48 which keeps track of critical components and runs algorithms for proper functioning of the device. A wireless device, such as a Bluetooth module 54 on the CCA, communicates with the micro-controller, and enables the device to connect with other Bluetooth enabled devices 56 . Optionally, the CCA incorporates a cellular modem 59 and/or GPS module 60 in a mother-daughter board arrangement.
[0039] A precise Real Time Clock (RTC) module 50 and a non-volatile memory (memory) 52 are other components of the preferred CCA; FIG. 10 . When the embodiment wakes up from the low power sleep state the time and date are obtained from the RTC for use in the rolling access code calculation algorithm. When the embodiment is locked, unlocked or tampering is detected the time and date are obtained from the RTC for notating the date and time of the event (time-stamping) in the event log stored in memory. The event log, manifest, user settings, random code generation tables (E-Code) and device specific information such as the unique device serial number are stored in the memory for future retrieval.
[0040] In preferred embodiments, the Real-Time Clock is the principal link between the rolling access code server and the lock. The rolling access code is generated as a function of Date, Time, DSN, E-Code Lookup Table. The Real-Time Clock also provides time-stamping for the Events in the Event Log. With the time stamp, the container can be traced to a specific location or condition at a specific time. For example, a tamper event at 0100 on the 25 th of February verifies that the container was in the possession of a particular shipping company. If a theft loss is not discovered until days later after the container has passed through multiple transportation companies, the date of the theft can be verified and a claim filed against the transportation company then in possession.
[0041] The Non-Volatile Memory may store user settings, such as the Code Validity Period, the event log, such as lock, unlock, and tamper events, and a shipping manifest.
[0042] An H-bridge solenoid driver circuit may be used to operate the solenoid.
[0043] The embodiment as shown in FIG. 1 is preferred to be a wireless device, which may be a Bluetooth Enabled Device (BED). In this embodiment, a BED and the correct Bluetooth access (pairing) code are required. When the embodiment is locked, it may enter a low power state after a prescribed time period; for example 30 seconds. The button 62 on the HMI 44 is pushed to activate the device and put the Bluetooth module 54 in discovery mode. The blue LED on the HMI starts blinking to indicate that embodiment is in discovery mode and ready to be paired. This embodiment now shows up on the Bluetooth Device list of any BED in close vicinity. The user can pair their BED with the embodiment, thereby unlocking the embodiment. When the embodiment is successfully unlocked, time and date from the RTC are obtained and the unlock event may be stored in memory. The Media Access Control (MAC) Address of the unlocking BED may also be stored during the unlock event.
[0044] In one embodiment, the device incorporates a Rolling Access Code scheme that dynamically changes the access (pairing) code based on a pre-defined Code Validity Period (CVP). If a Bluetooth device is used, dynamic changes to the pairing code are provided. Each lock is given a unique Device Serial Number (DSN) and this serial number is saved to the memory present in the lock. The processor of the device may also have a set of code generation tables, each table containing random numbers (E-Code), also stored in memory; for example, 10 pages of 365 tabulated random 8-digit numbers. When CVP expires, the device of this embodiment changes its code, such as the Bluetooth access (pairing) code, thereby rendering the previous code ineffective. For example, if the CVP is defined as 1 hour, at the top of each hour the embodiment changes its Bluetooth access code. A user who obtains the access code within the hour will not be able to use the same code after the top of the next hour.
[0045] In a preferred embodiment, the Rolling Access Code (RAC) is determined by a RAC generation algorithm executed by the microcontroller. The effective RAC is computed as a function of the current date and time (T-Code), as provided by the RTC, the unique DSN, as retrieved from memory, and an E-Code selected from a particular code generation table based; for example, on the DSN and the current date. The RAC generation algorithm is suitably designed to negate the affects of numerical calculation errors such as rounding. The RAC generation algorithm may resemble the following function: F(T-Code * E-Code * DSN)=RAC. A preferred embodiment accepts only a 6 -digit Bluetooth pairing code, thereby, providing elimination of accidental pairing with other BEDs employing the standard 4-digit Bluetooth pairing code.
[0046] In a preferred embodiment, no external communication, such as communication to and from a satellite or cell tower, is required. Each device has a unique DSN and a precise RTC. This allows the current RAC to be calculated by a copy of the algorithm and E-Code tables operated at a location remote from the device, such as a computer server that also has precise date and time information. The current RAC may be obtained from the remote location by telephone or internet communications, and provided to an authorized user who will unlock the lock.
[0047] Once authentication of the user is established, for example by a user name and password, the user provides the DSN of the device to be unlocked to the remote location (server). The remote server verifies that the authenticated user is authorized to operate the particular device. For example, the remote server verifies that the provided DSN is within a set of DSNs controlled by the authenticated user's organization. The remote server calculates the current access code and provides the access code to the authenticated authorized user. When using a cellular ‘smart’ phone, a custom software application (app) may be used to connect to the server site via a Quick Response (QR) code printed on the HMI 8 . The smart phone may read the unique DSN via a bar code scanner, camera, Radio Frequency Identification (RFID) tag or similar technology. The application sends this information, along with the user's authentication information, to the secure source via a cellular network or WIFI network. Upon validation, the application transmits the access code to the device.
[0048] In a preferred embodiment, the device is equipped with a tilt sensor 65 . This sensor is preferred to be activated when the device is in the locked state. In this embodiment, when the device is locked on a container, it can be removed only after its unlocked using a wireless control such as a Bluetooth enabled device. If forced removal of the device from the container results in tilting of the device, any tilt above a predefined limit will be detected by the tilt sensor. For example, a tilt greater than 45 degrees to the original position of the device when locked will be detected by the tilt sensor. This detected tamper event is saved to the event log, with a time and date stamp, in the memory.
[0049] In a preferred embodiment, the device is equipped with a programmable shock sensor 66 . This sensor is preferred to be activated when the device is in the locked state. When the device is subject to high-g shock, such as from a hammer blow, the shock sensor registers this tamper event. This detected tamper event is saved to the event log, with a time and date stamp, in memory.
[0050] In a preferred embodiment, the device employs a J-Bar Tamper Detection Circuit 67 ; FIG. 5 . The J-Bar 6 is designed as one half of a closed electrical circuit and may employ two self-cleaning spring-loaded carbon brushes 78 connected to the CCA 46 to complete the other half of the circuit. The two sides of the stainless steel J-Bar are isolated over the length of the J-bar via a narrow slot 82 . At the U-Bar side of the device, the spacing of the J-bar isolation slot is maintained by a molded rubber spacer 25 . The factory installed spacer also prevents the J-Bar from being removed from the locking mechanism; positive stop. The J-Bar isolation slot is stress relieved with a circular hole. As an alternate embodiment, an isolated conductor, which may be—a nickel plated copper wire, is bonded to the J-Bar in a “U” shaped channel, and the brushes ride on the conductor. The two brushes are mounted to a Printed Circuit Board (PCB). The PCB, mounted to the J-bar guide of the locking mechanism, provides mechanical alignment and electrical connection to the brushes 78 . The self cleaning spring-loaded carbon brushes maintain electrical contact with the J-Bar as it is extended and retracted from the device. When in the locked state, the microcontroller 48 continually monitors the J-Bar tamper detection circuit continuity and logs a tamper event if an open circuit conditions is detected. Cutting the J-Bar will result in an open circuit. This detected tamper event is saved to the event log, with a time and date stamp, in memory.
[0051] FIG. 8 shows the Audible Alarm Enunciator 60 which may be used by a preferred embodiment. As determined by the user settings, the audible alarm enunciator is activated when any tamper event is detected thereby drawing attention to the event.
[0052] In another embodiment, the memory of the circuit card assembly may comprise data logging 76 to store an inventory log of all goods on board (manifest). This inventory log may be made available only to users with administrative rights (administrators). Administrators can connect to the wireless or Bluetooth module via a Serial Port Profile (SPP) connection. Once this SPP connection is established administrators can download or upload data to the embodiment.
[0053] The circuit card assembly may be powered by rechargeable batteries 68 , such as Lithium Iron Phosphate batteries. These rechargeable batteries can be charged via the charging terminals 70 available on the embodiment. In the event of completely discharged batteries, the user can connect to an external battery 72 or battery charger 74 to the charging terminals to power the device and unlock the device as required.
[0054] FIG. 11 illustrates a tracking security function of another embodiment of the invention. A wireless transmitter 78 that is incorporated into the device transmits the current location of the device. A GPS receiving station 80 receives the location information from the transmitter, relays the location, for example, by internet 82 or cellular connection 84 to produce electronic mail, telephone or text messaging services. The GPS receiving station may upload location details to a mapping service database, which may be accessed as an internet website. In some applications, the device may communicate by radio, such as by communicating directly with the cellular system. Users may log into this website to track a container on a map. The device may communicate when accessed or send a distress signal when tampering is detected.
[0055] In the case of a wireless embodiment, such as a Bluetooth Enabled Device, upon access code entry and validation, the device may unlock, and log the event. In another embodiment, the device has a keypad or touchpad 12 as part of the HMI, which may be used to enter the temporary access code. The keypad or touchpad may be provided in addition to the wireless unlocking feature, and entry via this device may also be logged by the device.
[0056] Using a wireless connection or a hard-wired connection such as USB, authorized users may download the electronic manifest, container routing information, or other information, into the devices' on-board non-volatile memory. Law enforcement, border patrol or other agencies may access the manifest and the event log using proprietary software running on suitably equipped Bluetooth enabled computing device, such as a smart phone or tablet computer. Law enforcement can thereby be assured of the containers contents, last access date and time, and that the container has not been compromised.
[0057] Another embodiment incorporates wireless communication and/or Global Positioning System (GPS) technology onto the microcontroller board. The wireless communication may be traditional cellular technology and/or Short Burst Data Satellite Modem. Using the GPS or cellular network, this embodiment periodically determines the position of the secured container. An internal tracking algorithm determines if the secured container is within the dimensional bounds of the pre-programmed tracking, such as by position and time. Should the experienced track of the device and container violate the bounds of the expected track, an event is logged and the upgraded embodiment broadcasts an alert using the installed wireless network. A track violation occurs when the device is not within the scheduled grid established by the scheduled date and time.
[0058] In one embodiment, a wireless transmitter transmits location information on a frequent basis. A wireless receiving station on the other end receives the location. Pre-defined routes are downloaded to the wireless receiving station. With available route information and incoming information from the device, the wireless station determines if there is a route mismatch. The wireless receiving station notifies relevant parties, such as by telephone, e-mail or text messaging services. The wireless receiving station may upload location details to a mapping service, such as a website having mapping. Users can log track the subject container on a map. Wireless transmission and wireless reception means include, but are not limited to, Global Positioning Systems or modems.
[0059] In an embodiment, upon detection of a tamper event, the device transmits its location and all pertinent information, such as special manifest information, via the wireless communications network. | An electro-mechanical lock for cargo containers or similar enclosed spaces such as storage units. The locking mechanism includes a dual-ratcheting mechanism, which is normally in the locked position, and which firmly secures doors of a container or other enclosure. To unlock the device, the user obtains a temporary access code and unlocks the device, either by a wireless interface or by, for example, a key pad. The device incorporates a rolling access code algorithm that changes the access code based upon a pre-defined customer selected time period during which the code is valid. Once the validity period expires the user must obtain a new access code from a secure access code source to unlock the device. When access is desired, the user contacts a remote secure access code source, which provides the access code for the associated lock and time period. | 4 |
BACKGROUND
1. Field of the Invention
The present invention relates generally to test equipment, and more particularly to a system and method for verifying central office (CO) wiring associated with line sharing.
2. Background of the Invention
The Federal Communications Commission (FCC) has promulgated rules that require Incumbent Local Exchange Carriers (ILEC) to share certain telecommunications resources with Competitive Local Exchange Carriers (CLEC). One of these rules enables a CLEC to use telephone lines of an ILEC, in competition with the ILEC, to offer telecommunications services to customers of the ILEC. Such line sharing arrangement allows the CLEC to provide, for example, digital subscriber line (DSL) services over the same loop that is used by the ILEC for voice communications.
Without the line sharing arrangement, DSL services can be provided by the ILEC using a combined splitter and DSL modem (also known as a digital subscriber line access multiplexer or DSLAM) that are placed at a common location within a CO. Testing or verification of the wiring would not be a difficult task because both voice and data are provided by the ILEC. Under a line sharing arrangement, however, the CLEC's DSLAM is a different unit that is physically separated from the ILEC's splitter. Due to the competitive nature between the ILEC and the CLEC, the ILEC's splitter and the CLEC's DSLAM are physically located in different parts of a CO, even though each of the splitter and the DSLAM is ultimately connected to a common telephone line that serves the same customer. More often than not, the ILEC's splitter and the CLEC's DSLAM are located on separate floors in a building that houses the CO. Such physical separation of the splitter and the DSLAM creates unprecedented complexity associated with testing CO wiring. In some cases, for instance, five two-wire connections between wire terminals are required. This complexity, of course, increases the potential for wiring errors.
Portable telephone test sets are used extensively in the telecommunications industry to establish temporary communications or test lines for proper operation. These test sets are widely referred to as “butt sets.” The term butt sets is used herein to refer to the portable telephone test sets. As known in the art, voice circuits can be “verified” or tested using the CO's embedded Automatic Number Announcement Circuit (ANAC). The verification process typically involves the following steps. First, a technician bridges across the circuit with a conventional butt set. Second, the technician causes the butt set to go off-hook to draw a dial tone. Third, the technician dials the ANAC number. Fourth, the ANAC responds with the telephone number of the telephone line being tested. Fifth, the telephone number provided by the ANAC is used by the technician to verify the line. Unfortunately, this method of verification cannot be used to verify the DSL circuit in a line sharing arrangement in which the splitter and the DSLAM are physically separated.
To minimize the possibility of faults on the DSL circuit affecting the voice circuit, the industry standard for line sharing requires a blocking capacitor in the splitter. As known in the art, the blocking capacitor prevents the flow of direct current, which signals the switch to provide dial tone. For this reason, the ANAC process described above cannot be used.
There are currently no known products on the market that are specifically designed to verify the DSL circuit under the line sharing arrangement. As a result, technicians of local exchange carriers must improvise a method to verify CO wiring associated with line sharing.
Technicians have attempted to verify the DSL circuit using frequencies higher than those in the voice band to overcome the blocking capacitor. This method is undesirable because it requires a transmitter and a specially made receiver that is adapted to detect high frequencies. A conventional butt set cannot be used as the receiver in this method. The use of the transmitter and the special receiver to verify CO wiring is not considered to be cost-effective. In some situations, several special receivers per CO may be necessary, making this solution more expensive and even less desirable.
Accordingly, there is a need for a system and method that can verify the DSL circuit in a line sharing arrangement in a cost effective manner. Specifically, there is a need for a system and method that can utilize existing conventional butt sets to verify the DSL circuit in a line sharing arrangement.
SUMMARY OF THE INVENTION
The present invention is a system and method that uses amplitude modulation to verify the DSL circuit in a shared telephone line. The system of the invention includes a transmitter and a receiver. The transmitter sends an amplitude-modulated test signal to the shared telephone line. The test signal is introduced to the telephone line on one side of a blocking capacitor that isolates a DSLAM on the DSL circuit. The test signal is a product of a high frequency carrier signal and a low frequency audible signal. The receiver is connected to the DSL circuit of the shared telephone line on the other side of the blocking capacitor to detect the test signal. The DSL circuit is verified if the test signal is detected by the receiver through the blocking capacitor.
In a preferred embodiment of the invention, a conventional butt set is used as the receiver. It is noted that most conventional butt sets have enough non-linearity to detect the signal. In instances in which newer butt sets (designed with better linearity) are employed, an external detector may be employed. The transmitter has an amplitude modulator that mixes the audible signal received from a low frequency oscillator and a carrier signal received from a high frequency oscillator. The product of the amplitude modulator is the amplitude-modulated test signal.
The carrier signal generated by the high frequency oscillator could have a frequency as low as a few tens of kHz, below which the filtering described below would be difficult. It could have a frequency as high as a few tens of MHz, above which the attenuation of the wiring and cabling through which the signal must pass might be excessive. Preferably, the carrier signal is in the range of about 25 kHz to about 1 MHz, the same range of frequencies used by ADSL. At about 100 kHz, the frequency of the carrier signal is high enough that the signal is transmitted through the blocking capacitor and low enough that the signal is not unduly attenuated by the wiring and cabling through which it must pass.
In the preferred embodiment, the audible signal generated by the low frequency oscillator preferably has a frequency at between about 300 Hz and about 3 kHz. Preferably, the audible signal is at about 1 kHz. Preferably, a gate or a switch is provisioned between the low frequency oscillator and the amplitude modulator to regulate the input of the low frequency signal to the amplitude modulator at a low rate, for example, less than about 5 Hz. For example, the gate opens at a rate of about two times per second. This rate is desirable because it produces a tone that is distinguishable by a technician during verification.
The test signal generated by the amplitude modulator is then processed by a high-pass filter to remove any residual low frequency signals before it is used to verify the DSL circuit. Preferably, the transmitter is also equipped with a low-pass filter to prevent the remaining high frequency components of the test signal from going to the outside plant or the customer side of the telephone line. This allows the customer to use the telephone line for voice communications without interruption. The test signal that goes to the CO side of the telephone line does not go through the low-pass filter in the transmitter. As a result, the high frequency test signal goes from the transmitter to the CO side of the telephone line.
Preferably, the test signal is output from the transmitter to a main distributing frame of the CO to test the telephone line. The test signal goes through the main distributing frame to a splitter having a blocking capacitor and a low-pass filter, which are connected to the DSLAM and a voice switch, respectively. Since the test signal has a high frequency carrier component, the test signal can go through the blocking capacitor to verify the DSL circuit. A receiver placed on the other side of the blocking capacitor then verifies the presence of the test signal on the DSL circuit. The low-pass filter in the splitter ensures that the test signal does not interrupt the voice circuit part of the telephone line.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of the present invention.
FIG. 2 is a schematic diagram showing the system architecture of an embodiment of a transmitter of the present invention.
FIG. 3 is a flowchart showing exemplary steps used to practice an embodiment of the present invention.
FIG. 4 is a flowchart showing exemplary steps used in implementing an embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 is a schematic diagram showing a high level view of the present invention. Telephone line 110 is associated with customer 120 for voice and data communication services that are provided by an ILEC and a CLEC, respectively. Customer 120 uses CPE 122 for voice sessions and computer 124 for data sessions. Under the line sharing arrangement, the data sessions are handled by the CLEC that owns DSLAM 130 , and the voice sessions are processed by the ILEC that uses switch 140 . Both voice and data sessions go through main distributing frame 160 at CO 100 .
The line sharing arrangement comprises splitter 150 , which is connected to DSLAM 130 and switch 140 as shown in FIG. 1 . Splitter 150 is provisioned on telephone line 110 to separate voice and data components of telephone line 110 . The voice component is processed by the ILEC through switch 140 . The data component is processed by DSLAM 130 , which is owned and operated by the CLEC. As required by the industry standard, blocking capacitor 154 is required to separate DSLAM 130 so that interference created by the CLEC's DSL circuit will not affect the POTS circuit of the ILEC. Blocking capacitor 154 also makes it impossible to test the DSL circuit using conventional voice band frequencies.
As shown in FIG. 1, blocking capacitor 154 is a component of splitter 150 that separates DSLAM 130 from main distributing frame 160 . In addition to blocking capacitor 154 , splitter 150 has low-pass filter 152 that connects switch 140 to main distributing frame 160 .
System 300 is an embodiment of the present invention, which includes transmitter 200 and receiver 290 . Transmitter 200 sends a test signal to main distributing frame 160 at MDF connector 162 . Receiver 290 is connected to the DSL circuit at point 134 . Point 134 can be anywhere between DSLAM 130 and blocking capacitor 154 . The DSL circuit of telephone line 110 is verified if receiver 290 detects the test signal transmitted by transmitter 200 . In other words, the DSL circuit of telephone line 110 is complete when receiver 290 at point 134 can receive the test signal generated by transmitter 200 at MDF connector 162 .
FIG. 2 is a schematic diagram showing the system architecture of an embodiment of a transmitter of the present invention. As shown in FIG. 2, transmitter 200 includes amplitude modulator 210 , high-pass filter/balun 220 , low frequency oscillator 230 , high frequency oscillator 240 , low-pass filter 250 , and transmitter connector 260 . A balun is a device that converts a circuit from balanced to unbalanced (BAL UN) and vice versa. Note that the input to high-pass filter/balun 220 is unbalanced, i.e., referenced to ground, while the output of high-pass filter/balun 220 is balanced, i.e., the signal is applied across paths 222 and 224 and is not referenced to ground.
Amplitude modulator 210 receives an audible signal (the interfering signal) from low frequency oscillator 230 and a carrier signal from high frequency oscillator 240 to produce an amplitude-modulated test signal. The low frequency signal can be at a frequency between about 300 Hz and about 3 kHz. Preferably, the low frequency audible signal is at about 1 kHz. The audible signal is preferably regulated by gate 232 . Preferably, gate 232 opens at a rate of about two times per second. This rate enables a field technician to hear the audible signal through receiver 290 at point 134 (see FIG. 1 ).
The carrier signal generated by high frequency oscillator 240 can be at a frequency as low as a few tens of kHz, below which the filtering described below would be difficult. The carrier signal could have a frequency as high as a few tens of MHz, above which the attenuation of the wiring and cabling through which the signal must pass might be excessive. Preferably, the carrier signal is in the range of about 25 kHz to about 1 MHz, the same range of frequencies used by ADSL. At about 100 kHz, the frequency of the carrier signal is high enough that the signal is transmitted through the blocking capacitor and low enough that the signal is not unduly attenuated by the wiring and cabling through which it must pass. The 100 kHz frequency has been tested to couple through blocking capacitor 154 in splitter 150 (see FIG. 1 ).
The amplitude-modulated test signal output by amplitude modulator 210 is processed by high-pass filter/balun 220 . High-pass filter/balun 220 removes any residual low frequency signal that is output by amplitude modulator 210 .
Transmitter connector 260 is, for example, a five-pin connector that is adapted to mate with MDF connector 162 at main distributing frame 160 (see FIG. 1 ). Preferably, a test signal coming out of high-pass filter/balun 220 on paths 222 and 224 is balanced and is sent to the CO side of the telephone line through the short pins of transmitter connector 260 (see paths 274 and 284 ). Preferably, the test signal coming out of high-pass filter/balun 220 on paths 222 and 224 is split at nodes 270 and 280 , respectively, so that the test signal can be further blocked by low-pass filter 250 before it is sent to the outside plant side of the telephone line through the long pins of transmitter connector 260 (see paths 272 and 282 ).
Referring to FIG. 1, splitter 150 has low-pass filter 152 that prevents the high-frequency test signal from being coupled into the voiceband switch 140 , thus preventing unwanted IMD from occurring in switch 140 . Similarly, low-pass filter 250 in transmitter 200 prevents the IMD in CPE 122 . Thus, the present invention permits the use of high frequency test signal to verify the DSL circuit without interrupting the voice circuit.
An exemplary implementation of the transmitter of the present invention has the following characteristics.
1: The transmitter is a hand-held unit powered by one or more 9-volt batteries.
2: The transmitter is connected at the main distributing frame of a CO so that low-pass filtering that is needed to prevent the creation of voiceband noise via the IMD in the CPE can be employed.
3: The transmitter has a five-pin plug or connector that is capable of being inserted into a conventional five-pin protector jack at the main distributing frame. For older style frames, alligator clips can be provided.
4: The transmitter is capable of supporting itself by the connecting cord, such that it will not pull out the five-pin plug.
5: The case of the transmitter is made of a non-metallic material. Non-metallic materials are used so that the transmitter does not “short” or otherwise interfere with other subscriber lines on the MDF.
6: A non-metallic strap is provided to support the case of the transmitter. Non-metallic materials are used so that the transmitter does not “short” or otherwise interfere with other subscriber lines on the MDF.
7. The test signal generated by the transmitter does not affect voice communication sessions of the telephone line.
8: While inserted into the five-pin plug, the transmitter completes the circuit between the outside plant and CO connections on the main distributing frame. A low-pass filter is required at the transmitter to isolate CPE from the high-frequency tone.
9: The direct current resistance between the outside plant side and the CO side (see FIG. 2) does not exceed 100 Ohms, measured at any level of current less than 100 mA. Compliance may be demonstrated by shorting the outside plant side and measuring the direct current resistance of the CO side.
10: The insertion loss of the transmitter (measured between the CO side and the outside plant side, between a 600 Ω source and load, and measured at 1004 Hz) does not exceed 1.5 dB.
11: The insertion loss of the transmitter (measured between the CO side and the outside plant side, between a 600 Ω source and load, and measured at 4004 Hz) does not exceed the insertion loss measured at 1004 Hz by more than 3.0 dB.
12: To be non-intrusive, the test signal transmitted toward the CLEC equipment is well out of the voiceband, but yet capable of being heard via detection, e.g., through non-linearities in a technician's butt set. It has been verified that a conventional butt set, when in the speaker-phone mode, can de-modulate the amplitude modulated 100 kHz carrier test signal. A nominal +9 dBm carrier modulated at about 80% produces a tone that is clearly audible even in a switchroom.
13: The transmitter transmits a signal consisting of a 100 kHz carrier amplitude modulated with an interrupted 1 kHz tone. The level of the carrier is +9 dBm, +/−1 dB, measured into 135 Ohms on the CO side. The modulation index is between 60 and 90%.
14: The transmitter does not introduce any significant level of noise into the voiceband itself (except, of course, when the butt set is connected).
15: The noise introduced into the voiceband does not exceed 20 dBrnC, measured into 900 Ohms, measured on either the CO side or the outside plant side.
16: The total wideband noise, measured across the outside plant side, does not exceed −60 dBm.
17: The above requirements are met with any level of direct current voltage between 0 and 105 V, applied across tip and ring on either the CO side or outside plant side.
18: The transmitter must not be damaged by the application of 20 Hz ringing, at 88 Vrms, superimposed on 55 Vdc, applied across tip and ring on either the CO side or the outside plant side.
19: When connected, the transmitter may be exposed to hazardous voltages, e.g., lightning, via the outside plant.
The transmitter is capable of working in the presence of up to 50 Vrms of induced-longitudinal voltage.
The transmitter exhibits at least 55 dB of longitudinal balance, measured using the IEEE method, at any frequency between 60 Hz and 4 kHz.
The transmitter is equipped with normal over-voltage protection.
20: The transmitter should not provide a false “trouble” indication to a loop test system.
The direct current resistance, between any combination of tip, ring, and ground, shall exceed 3.5 MΩ.
The capacitance to ground, from either tip or ring, does not exceed 1.0 nF.
FIG. 3 is a flowchart showing exemplary steps involved in using an embodiment of the present invention.
In step 302 , a transmitter of the present invention is connected to a main distributing frame at which a shared telephone line is present.
In step 304 , a high frequency oscillator generates a carrier signal.
In step 306 , an amplitude modulator of the transmitter mixes the high frequency carrier signal with a low frequency audible signal to produce an amplitude-modulated test signal.
In step 308 , any residual low-frequency signal output by of the amplitude modulator is removed by a high-pass filter in the transmitter.
In step 310 , the amplitude-modulated test signal is sent to a splitter at the CO side of the telephone line via the main distributing frame.
In step 312 , a receiver of the present invention is connected to the DSL circuit on the other side of the splitter which is isolated by a blocking capacitor.
In step 314 , the DSL circuit is verified if the receiver detects the test signal.
FIG. 4 is a flowchart showing exemplary steps involved in implementing an embodiment of the present invention.
In step 402 , a high frequency signal is introduced to an amplitude modulator by a high frequency oscillator. The high frequency signal preferably has a frequency between about 10 kHz and about 10 MHz.
In step 404 , the amplitude modulator mixes the high frequency signal with a low frequency signal. The high frequency signal is amplitude modulated as the carrier signal to carry the audible low frequency signal. The low frequency signal is introduced to the amplitude modulator by a low frequency oscillator. The low frequency signal is in the voice band which is audible by a human. The low frequency signal preferably has a frequency between about 300 Hz and about 3 kHz.
In step 406 , any residual low frequency signal output by the amplitude modulator is removed by a high-pass filter.
In step 408 , the amplitude-modulated test signal is introduced to the telephone line at the main distributing frame side of the blocking capacitor.
In step 410 , a receiver of the invention is used to detect the test signal at the DSLAM side of the blocking capacitor.
It is noted that the transmitter could be connected to the MDF via an automated means of interconnection, so as to minimize the labor required to locate the line to be tested and connect the instrument. Alternatively, this invention could also be implemented by permanently incorporating the transmitter in the splitter or in the DSLAM. In either arrangement an automated mechanism (for connecting the transmitter to the circuit to be tested) could be employed so as minimize the number of transmitters required. In this implementation, the low pass filter (shown as item 250 in FIG. 2) would need to be removed so as to allow the high-frequency signal to be transmitted toward the MDF.
The foregoing disclosure of the preferred embodiments of the present invention has been presented for purposes of illustration and description. It is not intended to be exhaustive or to limit the invention to the precise forms disclosed. Many variations and modifications of the embodiments described herein will be obvious to one of ordinary skill in the art in light of the above disclosure. The scope of the invention is to be defined only by the claims appended hereto, and by their equivalents.
Further, in describing representative embodiments of the present invention, the specification may have presented the method and/or process of the present invention as a particular sequence of steps. However, to the extent that the method or process does not rely on the particular order of steps set forth herein, the method or process should not be limited to the particular sequence of steps described. As one of ordinary skill in the art would appreciate, other sequences of steps may be possible. Therefore, the particular order of the steps set forth in the specification should not be construed as limitations on the claims. In addition, the claims directed to the method and/or process of the present invention should not be limited to the performance of their steps in the order written, and one skilled in the art can readily appreciate that the sequences may be varied and still remain within the spirit and scope of the present invention. | A system and method for verifying the integrity of a DSL circuit on a shared telephone line. The invention uses the amplitude modulation principles to overcome the difficulty associated with a blocking capacitor that isolates a DSLAM on the DSL circuit from the rest of the shared telephone line. A transmitter of the invention mixes a high frequency carrier signal and a low frequency audio signal to produce an amplitude-modulated test signal. The amplitude modulated signal is supplied to the telephone line at a main distributing frame side of the blocking capacitor and is detected by a receiver at the DSLAM side of the blocking capacitor. | 7 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of PCT/CN2009/073115, filed on Aug. 6, 2009. The contents of PCT/CN2009/073115 are all hereby incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of Invention
[0003] The present invention relates to a touch screen, and more particularly to a capacitive touch screen.
[0004] 2. Related Art
[0005] Touch is the most important sensory perception of human beings, and is the most natural way in human-machine interaction. The touch screen thus emerges and has already been widely applied in personal computers, smart phones, public information, intelligent household appliances, industrial control, and other fields. In the current touch field, the resistive touch screen, photoelectric touch screen, ultrasonic touch screen, and planar capacitive touch screen are mainly developed, and in recently years, the projected capacitive touch screen is developed rapidly.
[0006] So far, the resistive touch screen is still the mainstream product in the market. However, due to the double-layer substrate structure of the resistive touch screen, when the touch screen and the display panel are laminated in use, the reflection of the touch screen may greatly affect the display performance such as brightness, contrast, and chroma, thus greatly degrading the display quality, and the increase of the backlight brightness of the display panel may cause higher power consumption. The analog resistive touch screen has the problem of positioning drift, and needs calibration from time to time. In addition, the electrode contact working mode of the resistive touch screen also reduces the service life of the touch screen.
[0007] The display quality of the infrared touch screen and the ultrasonic touch screen is not affected. However, the cost of the infrared touch screen and the ultrasonic touch screen is high, and the water drop and dust may impair the working reliability of the touch screen. Particularly, due to their complicated structures and high power consumption, the infrared touch screen and the ultrasonic touch screen generally cannot be applied in portable products.
[0008] The planar capacitive touch screen has a single-layer substrate structure, and thus when the touch screen and the display panel are laminated in use, the touch screen only has a small impact on the display quality. However, the planar capacitive touch screen also has the problem of positioning drift, and needs to calibration from time to time. The water drop may also impair the working reliability of the touch screen. Particularly, due to its high power consumption and cost, the planar capacitive touch screen generally cannot be applied in portable products.
[0009] The projected capacitive touch screen may also have a single-layer substrate structure, and thus when the touch screen and the display panel are laminated in use, the touch screen only has a small impact on the display quality. However, the projected capacitive touch screen detects the position of the finger or other touch objects on the touch screen by measuring the influence of the finger or other touch objects on the coupling capacitance between the electrodes of the touch screen, that is, by measuring the influence of the finger or other touch objects on the charging/discharging of the electrodes of the touch screen. The locating point is obtained through analog computation, and thus the projected capacitive touch screen is not a real digital touch screen. The distributed capacitance in the manufacturing and use environment may affect the working reliability of the touch screen, and the interference of the display driving signal and other electrical signals may influence the working of the touch screen, and the water drop may also impair the working reliability of the touch screen. In addition, the projected capacitive touch screen has a high requirement for the resistance of the detecting line, such that the detecting line of the projected capacitive touch screen laminated with the display panel in use needs to have not only a low electrical conductivity transparent electrode layer like ITO, but also a high electrical conductivity electrode layer like metal. Therefore, the manufacturing process is complicated, and the cost is high, especially for the large-sized and even ultra large-sized touch screens.
SUMMARY OF THE INVENTION
[0010] Accordingly, the present invention is directed to a real high-definition digital capacitive touch screen.
[0011] The basic working principle of the digital capacitive touch screen in the present invention is that, two staggered electrode groups are disposed on the touch substrate, multiple electrode lines of the electrode groups are connected to a touch excitation source, and the touch excitation source applies alternating current (AC) touch excitation signals to the electrode lines. When a finger of a human being or other touch objects approach to or touch a certain electrode line, the finger or other touch objects form a coupling capacitance with the electrode, and thus the touch excitation signal on the electrode line is leaked through the coupling capacitance. A touch system circuit detects the variances of the touch signals on the electrode lines to find the electrode lines having a maximum leakage current or having a leakage current exceeding a threshold, so as to determine the position of the finger or other touch objects on the touch substrate.
[0012] In the present invention, the touch excitation signals are applied to the multiple electrode lines at the same time, such that the cross-talk and flowing of the touch signals between the detecting lines and between the detecting lines and the non-detecting lines are reduced, and the flowing direction of the touch signals is controlled, so as to enhance the accuracy of determining the touched electrodes, and achieve a real digital capacitive touch screen.
[0013] In the digital capacitive touch screen of the present invention, the touched electrode lines are determined by detecting relative values of the variances of the touch signals on the electrode lines, thereby lowering the requirement for the resistance of the electrode lines, and realizing large-sized and even ultra large-sized capacitive touch screens.
[0014] The following technical solution is provided to solve the technical problems of the present invention.
[0015] A digital capacitive touch screen includes a touch substrate and a touch system circuit. The touch system circuit has a touch excitation source and a touch signal detection unit. At least two staggered electrode groups are disposed on the touch substrate, and multiple electrode lines of the electrode groups are connected to the touch excitation source. In a working period of the touch system circuit, for at least one moment, the touch excitation source applies touch signals to more than two electrode lines at the same time, and the touch signal detection unit selects at least one shielded electrode line as a detecting line. The detecting line detects the change of the touch signal flowing through the electrode when the touch signal is applied to the electrode. The shielded electrode refers to the electrode where the adjacent or non-adjacent electrode lines on two sides of the electrode line are applied with the touch signals, or the electrode where the electrode lines staggered with the electrode line are applied with the touch signals.
[0016] The following technical solutions are further provided to solve the technical problems of the present invention.
[0017] In a specific implementation of the present invention, a part of the electrode lines are selected as the detecting lines at each moment, the non-detecting lines are also applied with the touch signals when the detecting lines are applied with the touch signals, and the changes of the touch signals on the detecting lines are detected; the non-detecting lines applied with the touch signals are all of or a part of the non-detecting lines among the electrode lines connected to the touch system circuit except for the detecting lines.
[0018] In a specific implementation of the present invention, when the detecting lines are applied with the touch signals and the changes of the touch signals flowing through the detecting lines are detected, the other electrodes staggered with the detecting lines are also applied with the touch signals; the other electrodes staggered with the detecting lines are all of or a part of the electrodes staggered with the detecting lines.
[0019] In a specific implementation of the present invention, when the detecting lines are applied with the touch signals and the changes of the touch signals flowing through the detecting lines are detected, the other electrodes not staggered with the detecting lines are also applied with the touch signals; the other electrodes not staggered with the detecting lines are all of or a part of the electrodes not staggered with the detecting lines.
[0020] In a specific implementation of the present invention, when the detecting lines are applied with the touch signals and the changes of the touch signals flowing through the detecting lines are detected, the other electrodes staggered or not staggered with the detecting lines are also applied with the touch signals; the other electrodes staggered or not staggered with the detecting lines are all of or a part of the electrodes staggered or not staggered with the detecting lines.
[0021] In a specific implementation of the present invention, the touch signals output by the touch system circuit to the electrode lines are AC signals having frequencies not smaller than 50 KHz, including AC signals with zero amplitude.
[0022] In a specific implementation of the present invention, the touch signals applied on the electrodes share the same amplitude, phase, frequency, or serial number.
[0023] In a specific implementation of the present invention, the touch signals applied on the electrodes vary in at least one of the amplitude, phase, frequency, and serial number.
[0024] In a specific implementation of the present invention, when selecting the detecting lines, the touch system circuit selects a part of the display screen electrode lines as a detecting line group at a moment, and detects the changes of the touch signals flowing through the detecting lines.
[0025] In a specific implementation of the present invention, when selecting the detecting lines, the touch system circuit selects two or more parts of the electrode lines as two or more detecting line groups at the same moment, and respectively detects the changes of the touch signals flowing through the detecting line groups.
[0026] In a specific implementation of the present invention, each detecting line group is formed by one or more electrode lines.
[0027] In a specific implementation of the present invention, the touch system circuit selects the detecting lines in a scanning manner, so as to select different parts of the electrode lines as the detecting lines at different moments.
[0028] In a specific implementation of the present invention, the touch system circuit detects current signals and/or voltage signals in the detection of the touch signals on the electrode lines.
[0029] In a specific implementation of the present invention, the touch system circuit detects at least one of amplitude, time, phase, frequency signal, and pulse number in the detection of the touch signals on the electrode lines.
[0030] In a specific implementation of the present invention, the touch system circuit determines the touched electrode lines by detecting the touch signals or detecting differences between variances of the touch signals or variation rates of touch signals on the electrode lines.
[0031] In a specific implementation of the present invention, in order to more precisely determine the position of the touch object or reduce the number of the electrode lines connected to the touch system circuit on the touch substrate, the touch system circuit computes and determines the touched positions of the touch object among the electrode lines by detecting the touch signals or detecting differences between variances of the touch signals or variation rates of the touch signals on the electrode lines.
[0032] In a specific implementation of the present invention, the positions where the touch signals are detected or it is detected that the variances of the touch signals or the variation rates of the touch signals are maximum are determined as the touched positions, the positions where the touch signals are detected or it is detected that the variances of the touch signals or the variation rates of the touch signals exceed a preset threshold are determined as the touched positions, or the positions where the touch signals are detected or it is detected that the variances of the touch signals or the variation rates of the touch signals are maximum and exceed a preset threshold are determined as the touched positions.
[0033] In a specific implementation of the present invention, the electrode groups connected to the touch system circuit on the touch substrate are two orthogonal electrode groups.
[0034] In a specific implementation of the present invention, each electrode line connected to the touch system circuit on the touch substrate has an edge in the shape of a fold line, and two adjacent linear segments of the fold line form an angle ranging from 20° to 160°.
[0035] In a specific implementation of the present invention, the electrodes on the touch substrate include not only the electrode lines connected to the touch system circuit but also the electrode lines not connected to the touch system circuit.
[0036] In a specific implementation of the present invention, the at least two staggered electrode groups on the touch substrate are disposed on different substrates.
[0037] In a specific implementation of the present invention, the at least two staggered electrode groups on the touch substrate are disposed on different layers isolated by an insulation layer of the same substrate.
[0038] In a specific implementation of the present invention, the touch substrate is disposed with a shielded electrode insulated from the staggered electrode groups.
[0039] In a specific implementation of the present invention, the electrode lines connected to the touch system circuit on the touch substrate are disposed on a touch surface of the touch substrate.
[0040] In a specific implementation of the present invention, the electrode lines connected to the touch system circuit on the touch substrate are disposed on a non-touch surface of the touch substrate.
[0041] In a specific implementation of the present invention, the touch substrate is a flexible or rigid transparent substrate.
[0042] The present invention has the following beneficial effects compared with the prior art.
[0043] The present invention provides a high-definition digital capacitive touch screen. In the capacitive touch screen of the present invention, the touch signals are applied to the detecting lines and the non-detecting lines at the same time, so as to reduce the flowing of the touch signals between the detecting lines and between the detecting lines and the non-detecting lines, and control the flowing direction of the touch signals, such that the accuracy of determining the touched electrodes is enhanced to recognize each electrode line, and a real digital capacitive touch screen is achieved.
[0044] The amplitude, phase, frequency, or serial number of the touch signals applied to the detecting lines may be adjusted to different values, and the amplitude, phase, frequency, or serial number of the touch signals applied to the non-detecting lines may also be adjusted to be different from the amplitude, phase, frequency, or serial number of the touch signals applied to the detecting lines, so as to more precisely control the flowing direction of the touch signals.
[0045] The present invention provides a large-sized capacitive touch screen. In the digital capacitive touch screen of the present invention, the touched electrode lines are determined by detecting the touch signals or detecting differences between variances of the touch signals or variation rates of the touch signals on the electrode lines, that is, by detecting the relative values of the touch signals on the electrode lines. Thus, the requirement for the resistance of the electrode lines is not high, and the touched electrode lines can still be accurately determined by measuring the relative values of the touch signals on the electrode lines when the resistance of the electrode lines is increased due to the extension of the electrode lines in a large-sized touch screen, thereby achieving a large-sized and even ultra large-sized capacitive touch screen.
[0046] Regarding the conditions for determining the touched electrode lines, the electrode lines where it is detected that the variances of the touch signals are maximum and exceed a preset threshold are determined as the touched electrode lines, and the touch flat panel display adopts a single-point touch mode. Regarding the conditions for determining the touched electrode lines, the electrode lines where it is merely detected that the variances of the touch signals exceed a preset threshold may also be determined as the touched electrode lines, so that the digital capacitive touch screen of the present invention supports a multi-point touch mode.
[0047] The digital capacitive touch screen of the present invention has a simple structure, and can be easily obtained through the current manufacturing process of the display and the touch screen, so that the touch screen has a low cost and high reliability.
BRIEF DESCRIPTION OF THE DRAWINGS
[0048] FIG. 1 is a schematic view of electrical connection according to a first embodiment, a second embodiment, and a third embodiment of the present invention;
[0049] FIG. 2 is a schematic view of electrical connection according to a fourth embodiment and a fifth embodiment of the present invention;
[0050] FIG. 3 is a schematic structural view according to a sixth embodiment of the present invention;
[0051] FIG. 4 is a schematic structural view according to a seventh embodiment of the present invention;
[0052] FIG. 5 is a schematic structural view according to an eighth embodiment of the present invention;
[0053] FIG. 6 is a schematic structural view according to a ninth embodiment of the present invention; and
[0054] FIG. 7 is a schematic structural view according to a tenth embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
FIRST EMBODIMENT
[0055] The digital capacitive touch screen 100 as shown in FIG. 1 includes a touch panel 110 and a touch system circuit 140 . A row electrode group 120 (including row electrode lines 121 , 122 , . . . , 12 m ) and a column electrode group 130 (including column electrode lines 131 , 132 , . . . , 13 n ) arranged orthogonal to each other are disposed on the touch panel 110 . The touch system circuit 140 has a row touch system circuit 141 , a column touch system circuit 142 , and a control and determination circuit 143 . Multiple electrode lines of the row electrode group 120 are connected to the row touch system circuit 141 , multiple electrode lines of the column electrode group 130 are connected to the column touch system circuit 142 , and the row touch system circuit 141 and the column touch system circuit 142 are both connected to the control and determination circuit 143 . The touch system circuit includes a row touch system circuit and a column touch system circuit, each including a touch excitation source and a touch signal detection unit. In the subsequent description of this embodiment as well as the description of other embodiments, the touch excitation source and the touch signal detection unit may not be specified and will be collectively referred to as the “touch system circuit”, “row touch system circuit”, or “column touch system circuit”.
[0056] Firstly, the touch system circuit 140 performs touch detection on the row electrode group 120 . The row touch system circuit 141 selects all the row electrode lines 121 , 122 , . . . , 12 m of the row electrode group 120 as row detecting lines, and applies touch signals to all the row electrode lines at the same time. The column touch system circuit 142 also applies the same touch signals to all the column electrode lines of the column electrode group 130 as those applied by the row touch system circuit 141 to the row electrodes. The row touch system circuit 141 also detects the changes of the touch signals flowing through the row electrode lines respectively, and the control and determination circuit 143 determines the row electrode lines where the row touch system circuit 141 detects that the variances of the touch signals flowing through are maximum and exceed a preset threshold as the touched row electrode lines. Then, the touch system circuit 140 performs touch detection on the column electrode group 130 . The column touch system circuit 142 selects all the column electrode lines 131 , 132 , . . . , 13 n of the column electrode group 130 as column detecting lines, and applies touch signals to all the column electrode lines at the same time. The row touch system circuit 141 also applies the same touch signals to all the row electrode lines of the row electrode group 120 as those applied by the column touch system circuit 142 to the column electrodes. The column touch system circuit 142 detects the changes of the touch signals flowing through the column electrode lines respectively, and the control and determination circuit 143 determines the column electrode lines where the column touch system circuit 142 detects that the variances of the touch signals flowing through are maximum and exceed a preset threshold as the touched column electrode lines. The touch system circuit 140 repeatedly and alternately performs touch detection on the row electrode group 120 and the column electrode group 130 , and determines the positions of the touched points according to cross-points of the detected touched row electrode lines and the detected touched column electrode lines, so as to form a digital capacitive touch screen capable of recognizing m×n touch points.
[0057] Regarding the conditions for determining the touched electrode lines, the electrode lines where it is detected that the variances of the touch signals flowing through are maximum and exceed a preset threshold may not be determined as the touched electrode lines. Instead, the positions of the first three electrode lines where it is detected that the variances of the touch signals flowing through exceed a preset threshold are weighted by an average value of the variances of the touch signals to obtain the touch position, and the computed touch position is generally not located at the center of a certain electrode line, thus achieving a digital capacitive touch screen with higher precision capable of recognizing over m×n touch points.
[0058] In order to make the variances of the touch signals large enough when the operator touches the digital capacitive touch screen to resist the interference for ease of measurement, the touch signals need to have sufficient penetrating power, and the frequencies of the touch signals output by the touch system circuit to the electrode lines are not smaller than 50 KHz.
[0059] In the detection of the touch signals on the electrode lines, the touch system circuit may detect voltage signals and/or current signals, and may also detect amplitude, phase, frequency signal, or pulse number recorded by a counter during the charging/discharging time period of the electrode lines to the capacitor.
[0060] Regarding the conditions for determining the touched electrode lines, the electrode lines where it is merely detected that the variances of the touch signals flowing through exceed a preset threshold may also be determined as the touched electrode lines, so that the digital capacitive touch screen supports a multi-point touch mode.
SECOND EMBODIMENT
[0061] The digital capacitive touch screen 100 as shown in FIG. 1 includes a touch panel 110 and a touch system circuit 140 . A row electrode group 120 (including row electrode lines 121 , 122 , . . . , 12 m ) and a column electrode group 130 (including column electrode lines 131 , 132 , . . . , 13 n ) arranged orthogonal to each other are disposed on the touch panel 110 . The touch system circuit 140 has a row touch system circuit 141 , a column touch system circuit 142 , and a control and determination circuit 143 . Multiple electrode lines of the row electrode group 120 are connected to the row touch system circuit 141 , multiple electrode lines of the column electrode group 130 are connected to the column touch system circuit 142 , and the row touch system circuit 141 and the column touch system circuit 142 are both connected to the control and determination circuit 143 .
[0062] The touch system circuit 140 performs touch detection on the row electrode group 120 and the column electrode group 130 simultaneously. The row touch system circuit 141 selects all the row electrode lines 121 , 122 , . . . , 12 m of the row electrode group 120 as row detecting lines, and applies touch signals to all the row electrode lines at the same time. The column touch system circuit 142 also applies the same touch signals to all the column electrode lines of the column electrode group 130 as those applied by the row touch system circuit 141 to the row electrodes. The row touch system circuit 141 also detects the changes of the touch signals flowing through the row electrode lines respectively, and the control and determination circuit 143 determines the row electrode lines where the row touch system circuit 141 detects that the variances of the touch signals flowing through are maximum and exceed a preset threshold as the touched row electrode lines.
[0063] Similarly, the column touch system circuit 142 selects all the column electrode lines 131 , 132 , . . . , 13 n of the column electrode group 130 as column detecting lines, and applies touch signals to all the column electrode lines at the same time. The row touch system circuit 141 also applies the same touch signals to all the row electrode lines of the row electrode group 120 as those applied by the column touch system circuit 142 to the column electrodes. The column touch system circuit 142 detects the changes of the touch signals flowing through the column electrode lines respectively, and the control and determination circuit 143 determines the column electrode lines where the column touch system circuit 142 detects that the variances of the touch signals flowing through are maximum and exceed a preset threshold as the touched column electrode lines. The touch system circuit 140 repeatedly performs touch detection on the row electrode group 120 and the column electrode group 130 , and determines the positions of the touched points according to cross-points of the detected touched row electrode lines and the detected touched column electrode lines, so as to form a digital capacitive touch screen capable of recognizing m×n touch points.
[0064] Regarding the conditions for determining the touched electrode lines, the electrode lines where it is detected that the variances of the touch signals flowing through are maximum and exceed a preset threshold may not be determined as the touched electrode lines. Instead, the positions of the first three electrode lines where it is detected that the variances of the touch signals flowing through exceed a preset threshold are weighted by an average value of the variances of the touch signals to obtain the touch position, and the computed touch position is generally not located at the center of a certain electrode line, thus achieving a digital capacitive touch screen with higher precision capable of recognizing over m×n touch points.
[0065] In the detection of the touch signals on the electrode lines, the touch system circuit may detect voltage signals and/or current signals, and may also detect amplitude, phase, frequency signal, or pulse number recorded by a counter during the charging/discharging time period of the electrode lines to the capacitor.
[0066] Regarding the conditions for determining the touched electrode lines, the electrode lines where it is merely detected that the variances of the touch signals flowing through exceed a preset threshold may also be determined as the touched electrode lines, so that the digital capacitive touch screen supports a multi-point touch mode.
THIRD EMBODIMENT
[0067] The digital capacitive touch screen 100 as shown in FIG. 1 includes a touch panel 110 and a touch system circuit 140 . A row electrode group 120 (including row electrode lines 121 , 122 , . . . , 12 m ) and a column electrode group 130 (including column electrode lines 131 , 132 , . . . , 13 n ) arranged orthogonal to each other are disposed on the touch panel 110 . The touch system circuit 140 has a row touch system circuit 141 , a column touch system circuit 142 , and a control and determination circuit 143 . Multiple electrode lines of the row electrode group 120 are connected to the row touch system circuit 141 , multiple electrode lines of the column electrode group 130 are connected to the column touch system circuit 142 , and the row touch system circuit 141 and the column touch system circuit 142 are both connected to the control and determination circuit 143 .
[0068] Firstly, the touch system circuit 140 performs touch detection on the row electrode group 120 . The row touch system circuit 141 selects one electrode line from the row electrode lines 121 , 122 , . . . , 12 m as a row detecting line in a scanning manner at each moment, applies a touch signal to the row detecting line, and detects the change of the touch signal flowing through the electrode line. Meanwhile, the row touch system circuit 141 also applies the same touch signals to all the row electrode lines of the rest non-detecting lines as that applied to the detecting line. The column touch system circuit 142 also applies the same touch signals to all the column electrode lines as that applied to the detecting line. The control and determination circuit 143 determines the row electrode lines where the row touch system circuit 141 detects that the variances of the touch signals flowing through are maximum and exceed a preset threshold as the touched row electrode lines. Then, the touch system circuit 140 performs touch detection on the column electrode group 130 . The column touch system circuit 142 selects one electrode line from the column electrode lines 131 , 132 , . . . , 13 n as a column detecting line in a scanning manner at each moment, applies a touch signal to the column detecting line, and detects the change of the touch signal flowing through the electrode line. Meanwhile, the column touch system circuit 142 also applies the same touch signals to all the column electrode lines of the rest non-detecting lines as that applied to the detecting line. The row touch system circuit 141 also applies the same touch signals to all the row electrode lines as that applied to the detecting line. The control and determination circuit 143 determines the column electrode lines where the column touch system circuit 142 detects that the variances of the touch signals flowing through are maximum and exceed a preset threshold as the touched column electrode lines. The touch system circuit 140 repeatedly and alternately performs touch detection on the row electrode group 120 and the column electrode group 130 , and determines the positions of the touched points according to cross-points of the detected touched row electrode lines and the detected touched column electrode lines, so as to form a digital capacitive touch screen capable of recognizing m×n touch points.
[0069] When the touch signal is applied to the detecting line, the amplitude, phase, or frequency of the touch signals applied to the non-detecting lines may be adjusted to be different from that of the touch signal applied to the detecting line, so as to more precisely control the flowing direction of the touch signals. Specifically, the touch signal applied to the detecting line may be different from those applied to the non-detecting lines in one or two items of the amplitude, phase, and frequency.
[0070] In the detection of the touch signals on the electrode lines, the touch system circuit may detect voltage signals and/or current signals, and may also detect amplitude, phase, frequency signal, or pulse number recorded by a counter during the charging/discharging time period of the electrode lines to the capacitor.
[0071] Regarding the conditions for determining the touched electrode lines, the electrode lines where it is detected that the variances of the touch signals flowing through are maximum and exceed a preset threshold may not be determined as the touched electrode lines. Instead, the positions of the first three electrode lines where it is detected that the variances of the touch signals flowing through exceed a preset threshold are weighted by an average value of the variances of the touch signals to obtain the touch position, and the computed touch position is generally not located at the center of a certain electrode line, thus achieving a digital capacitive touch screen with higher precision capable of recognizing over m×n touch points.
[0072] Regarding the conditions for determining the touched electrode lines, the electrode lines where it is merely detected that the variances of the touch signals flowing through exceed a preset threshold may also be determined as the touched electrode lines, so that the digital capacitive touch screen supports a multi-point touch mode.
[0073] To avoid a false touch, the control and determination circuit may not determine the following electrode lines as the touched electrode lines, that is, the electrode lines where although the row touch system circuit detects that the variances of the touch signals are maximum and exceed a preset threshold, the variation rates of the touch signals with time are too large (false touch for which the touch time is too short) or the variation rates of the touch signals with time are too small (false touch for which the touch time is too long).
FOURTH EMBODIMENT
[0074] The digital capacitive touch screen 200 as shown in FIG. 2 includes a touch panel 210 and a touch system circuit 240 . A row electrode group 220 (including row electrode lines 221 , 222 , . . . , 22 i , 22 i +1, . . . , 22 m ) and a column electrode group 230 (including column electrode lines 231 , 232 , . . . , 23 j , 23 j +1, . . . , 23 n ) arranged orthogonal to each other are disposed on the touch panel 210 . The touch system circuit 240 has a row touch system circuit 241 , a column touch system circuit 242 , and a control and determination circuit 243 . Multiple electrode lines of the row electrode group 220 are connected to the row touch system circuit 241 , multiple electrode lines of the column electrode group 230 are connected to the column touch system circuit 242 , and the row touch system circuit 241 and the column touch system circuit 242 are both connected to the control and determination circuit 243 .
[0075] Firstly, the touch system circuit 240 performs touch detection on the row electrode group 220 . The row touch system circuit 241 selects one electrode line from the row electrode lines 221 , 222 , . . . , 22 i as a detecting line and selects another electrode line from the row electrode lines 22 i +1, . . . , 22 m as a detecting line in a scanning manner at each moment, applies touch signals to the two detecting lines, and detects the changes of the touch signals flowing through the two electrode lines respectively. Meanwhile, the row touch system circuit 241 applies the touch signals of the same amplitude, phase, and frequency to all the row electrode lines of the rest non-detecting lines, and the column touch system circuit 242 also applies the touch signals of the same amplitude, phase, and frequency to all the column electrode lines. The control and determination circuit 243 determines the row electrode lines where the row touch system circuit 241 detects that the variances of the touch signals flowing through are maximum and exceed a preset threshold among all the row electrode lines 221 , 222 , . . . , 22 i , 22 i +1, . . . , 22 m as the touched row electrode lines. Then, the touch system circuit 240 performs touch detection on the column electrode group 230 . The column touch system circuit 242 selects one electrode line from the column electrode lines 231 , 232 , . . . , 23 j as a detecting line and selects another electrode line from the column electrode lines 23 j +1, . . . , 23 n as a detecting line in a scanning manner at each moment, applies touch signals to the two detecting lines, and detects the changes of the touch signals flowing through the two electrode lines respectively. Meanwhile, the column touch system circuit 242 applies the touch signals of the same amplitude, phase, and frequency to all the column electrode lines of the rest non-detecting lines, and the row touch system circuit 241 also applies the touch signals of the same amplitude, phase, and frequency to all the row electrode lines. The control and determination circuit 243 determines the column electrode lines where the column touch system circuit 242 detects that the variances of the touch signals flowing through are maximum and exceed a preset threshold among all the column electrode lines 231 , 232 , . . . , 23 j , 23 j +1, . . . , 23 n as the touched column electrode lines. The touch system circuit 240 repeatedly and alternately performs touch detection on the row electrode group 220 and the column electrode group 230 , and determines the positions of the touched points according to cross-points of the detected touched row electrode lines and the detected touched column electrode lines, so as to form a digital capacitive touch screen capable of recognizing m×n touch points.
[0076] As the row touch system circuit 241 and the column touch system circuit 242 both select two electrode lines as the detecting lines at the same time, and perform touch detection in separated regions at the same time in a scanning manner, the time required for detecting the touch points on the whole touch screen is reduced.
[0077] When the touch signals are applied to the detecting lines, the amplitude, phase, or frequency of the touch signals applied to the non-detecting lines may be adjusted to be different from those of the touch signals applied to the detecting lines, so as to more precisely control the flowing direction of the touch signals. Specifically, the touch signals applied to the detecting lines may be different from those applied to the non-detecting lines in one or two items of the amplitude, phase, and frequency.
[0078] Regarding the conditions for determining the touched electrode lines, the electrode lines where it is detected that the variances of the touch signals flowing through are maximum and exceed a preset threshold may not be determined as the touched electrode lines, and instead, the electrode lines where it is merely detected that the variances of the touch signals flowing through exceed a preset threshold may be determined as the touched electrode lines, so that the touch flat panel display supports a multi-point touch mode.
[0079] To avoid a false touch, the control and determination circuit may not determine the following electrode lines as the touched electrode lines, that is, the electrode lines where although the row touch system circuit detects that the variances of the touch signals are maximum and exceed a preset threshold, the variation rates of the touch signals with time are excessively large (false touch for which the touch time is too short) or the variation rates of the touch signals with time are excessively low (false touch for which the touch time is too long).
FIFTH EMBODIMENT
[0080] The digital capacitive touch screen 200 as shown in FIG. 2 includes a touch panel 210 and a touch system circuit 240 . A row electrode group 220 (including row electrode lines 221 , 222 , . . . 22 i , 22 i +1, . . . , 22 m ) and a column electrode group 230 (including column electrode lines 231 , 232 , . . . , 23 j , 23 j +1, . . . , 23 n ) arranged orthogonal to each other are disposed on the touch panel 210 . The touch system circuit 240 has a row touch system circuit 241 , a column touch system circuit 242 , and a control and determination circuit 243 . Multiple electrode lines of the row electrode group 220 are connected to the row touch system circuit 241 , multiple electrode lines of the column electrode group 230 are connected to the column touch system circuit 242 , and the row touch system circuit 241 and the column touch system circuit 242 are both connected to the control and determination circuit 243 .
[0081] Firstly, the touch system circuit 240 performs touch detection on the row electrode group 220 . The row touch system circuit 241 selects one electrode line from the row electrode lines 221 , 222 , . . . , 22 i as a detecting line and selects another electrode line from the row electrode lines 22 i +1, . . . , 22 m as a detecting line in a scanning manner at each moment, applies touch signals to the two detecting lines, and detects the changes of the touch signals flowing through the two electrode lines respectively. Meanwhile, the row touch system circuit 241 applies the touch signals of the same amplitude, phase, and frequency to all the row electrode lines of the rest non-detecting lines, and the column touch system circuit 242 also applies the touch signals of the same amplitude, phase, and frequency to all the column electrode lines. The control and determination circuit 243 determines the row electrode lines where the row touch system circuit 241 detects that the variances of the touch signals flowing through are maximum and exceed a preset threshold among the row electrode lines 221 , 222 , . . . , 22 i as the touched row electrode lines, and the control and determination circuit 243 also determines the row electrode lines where the row touch system circuit 241 detects that the variances of the touch signals flowing through are maximum and exceed a preset threshold among the row electrode lines 22 i +1, . . . 22 m as the touched row electrode lines. Then, the touch system circuit 240 performs touch detection on the column electrode group 230 . The column touch system circuit 242 selects one electrode line from the column electrode lines 231 , 232 , . . . , 23 j , 23 j +1, . . . 23 n as a detecting line in a scanning manner at each moment, applies a touch signal to the detecting line, and detects the change of the touch signal flowing through the electrode line. Meanwhile, the column touch system circuit 242 applies the touch signals of the same amplitude, phase, and frequency to all the column electrode lines of the rest non-detecting lines, and the row touch system circuit 241 also applies the touch signals of the same amplitude, phase, and frequency to all the row electrode lines. The control and determination circuit 243 determines the column electrode lines where the column touch system circuit 242 detects that the variances of the touch signals flowing through are maximum and exceed a preset threshold among all the column electrode lines 231 , 232 , . . . , 23 j , 23 j +1, . . . , 23 n as the touched column electrode lines. The touch system circuit 240 repeatedly and alternately performs touch detection on the row electrode group 220 and the column electrode group 230 , and determines the positions of the touched points according to cross-points of the detected touched row electrode lines and the detected touched column electrode lines, so as to form a digital capacitive touch screen capable of recognizing i×n touch points and (m−i)×n touch points in upper-half and lower-half regions of the touch panel 210 separated by the row electrode line 22 i.
[0082] When the touch signals are applied to the detecting lines, the amplitude, phase, or frequency of the touch signals applied to the non-detecting lines may be adjusted to be different from those of the touch signals applied to the detecting lines, so as to more precisely control the flowing direction of the touch signals. Specifically, the touch signals applied to the detecting lines may be different from those applied to the non-detecting lines in one or two items of the amplitude, phase, and frequency.
[0083] To avoid a false touch, the control and determination circuit may not determine the following electrode lines as the touched electrode lines, that is, the electrode lines where although the row touch system circuit detects that the variances of the touch signals are maximum and exceed a preset threshold, the variation rates of the touch signals with time are excessively large (false touch for which the touch time is too short) or the variation rates of the touch signals with time are excessively low (false touch for which the touch time is too long).
SIXTH EMBODIMENT
[0084] The touch panel 300 of the digital capacitive touch screen as shown in FIG. 3 includes an upper substrate 310 and a lower substrate 320 . The upper substrate 310 and the lower substrate 320 are bonded by an adhesive material 330 into one piece. A strip electrode group 340 formed by electrode lines 341 , 342 , . . . , 34 m each having an edge in the shape of a straight line is disposed on an inner side surface of the upper substrate 310 , and a strip electrode group 350 formed by electrode lines 351 , 352 , . . . , 35 n each having an edge in the shape of a straight line is disposed on an inner side surface of the lower substrate 320 . The electrode group 350 and the electrode group 340 are arranged perpendicular to each other. Extending ends of the electrode group 340 and the electrode group 350 for connection to a touch system circuit are respectively disposed on two perpendicular edges of the upper substrate 310 and the lower substrate 320 .
SEVENTH EMBODIMENT
[0085] When the touch panel 400 of the digital capacitive touch screen as shown in FIG. 4 is placed in front of a display in use, to reduce the influence of the touch panel 400 on the display effect to the maximum extent, a single transparent substrate 410 is adopted. A strip electrode group 420 formed by electrode lines 421 , 422 , . . . , 42 m each having an edge in the shape of a fold line is disposed on an upper side surface of the substrate 410 , and a strip electrode group 430 formed by electrode lines 431 , 432 , . . . , 43 n each having an edge in the shape of a fold line is disposed on a lower side surface of the substrate 410 . A center line of each electrode line in the electrode group 430 is arranged perpendicular to that of each electrode line in the electrode group 420 . Two adjacent linear segments of the fold line at the edge of each electrode line in the electrode group 420 and the electrode group 430 form an angle a ranging from 20° to 160°. Extending ends of the electrode group 420 and the electrode group 430 for connection to a touch system circuit are respectively disposed on two perpendicular edges of the substrate 410 . To prevent a user from directly touching the electrode group 420 , an insulation layer 440 is disposed on an external side of the electrode group 420 .
EIGHTH EMBODIMENT
[0086] When the touch panel 500 of the digital capacitive touch screen as shown in FIG. 5 is placed in front of a display in use, to reduce the influence of the touch panel 500 on the display effect to the maximum extent, a single transparent substrate 510 is adopted. A strip electrode group 520 formed by electrode lines 521 , 522 , . . . , 52 m and a strip electrode group 530 formed by electrode lines 531 , 532 , . . . , 53 n , each of the electrode lines having an edge in the shape of a straight line, are disposed on a non-touch surface of the substrate 510 . The electrode group 520 and the electrode group 530 are arranged on different layers and isolated by an insulation layer 540 . To enable the touch panel 500 to achieve a uniform transmittance when being placed in front of a display in use, a dispersed electrode group 550 is disposed at the same layer as the electrode group 520 in a region not covered by the projection of the electrode group 520 and the electrode group 530 on the surface of the substrate 510 . A center line of each electrode line in the electrode group 520 is arranged perpendicular to that of each electrode line in the electrode group 530 . Extending ends of the electrode group 520 and the electrode group 530 for connection to a touch system circuit are respectively disposed on two perpendicular edges of the substrate 510 .
NINTH EMBODIMENT
[0087] When the touch panel 600 of the digital capacitive touch screen as shown in FIG. 6 is placed in front of a display in use, to reduce the influence of the touch panel 600 on the display effect to the maximum extent, a single transparent substrate 610 is adopted. A strip electrode group 620 formed by electrode lines 621 , 622 , . . . , 62 m and a strip electrode group 630 formed by electrode lines 631 , 632 , . . . , 63 n , each of the electrode lines having an edge in the shape of a straight line, are disposed on a non-touch surface of the substrate 610 . The electrode group 620 and the electrode group 630 are arranged on different layers and isolated by an insulation layer 640 . To enable the touch panel 600 to achieve a uniform transmittance when being placed in front of a display in use, a dispersed electrode group 650 is disposed at the same layer as the electrode group 620 in a region not covered by the projection of the electrode group 620 and the electrode group 630 on the surface of the substrate 610 . A center line of each electrode line in the electrode group 620 is arranged perpendicular to that of each electrode line in the electrode group 630 . Extending ends of the electrode group 620 and the electrode group 630 for connection to a touch system circuit are respectively disposed on two perpendicular edges of the substrate 610 . To prevent the touch signals on the touch panel 600 from being interfered with by electrical signals in the display or machine, a shielded electrode 660 is additionally disposed on an internal side of the electrode group 630 , and is isolated from the electrode group 630 by an insulation layer 670 .
TENTH EMBODIMENT
[0088] When the touch panel 700 of the digital capacitive touch screen as shown in FIG. 7 is placed in front of a display in use, to reduce the influence of the touch panel 700 on the display effect to the maximum extent, a single transparent substrate 710 is adopted. A strip electrode group 720 formed by electrode lines 721 , 722 , . . . , 72 m and a strip electrode group 730 formed by electrode lines 731 , 732 , . . . , 73 n , each of the electrode lines having an edge in the shape of a straight line, are disposed on a touch surface of the substrate 710 . The electrode group 720 and the electrode group 730 are arranged on different layers and isolated by an insulation layer 740 . To prevent a user from directly touching the electrode group 730 , an insulation layer 760 is disposed on an external side of the electrode group 730 . Further, to enable the touch panel 700 to achieve a uniform transmittance when being placed in front of a display in use, a dispersed electrode group 750 is disposed at the same layer as the electrode group 730 in a region not covered by the projection of the electrode group 720 and the electrode group 730 on the surface of the substrate 710 . A center line of each electrode line in the electrode group 720 is arranged perpendicular to that of each electrode line in the electrode group 730 . Extending ends of the electrode group 720 and the electrode group 730 for connection to a touch system circuit are respectively disposed on two perpendicular edges of the substrate 710 . To prevent the touch signals on the touch panel 700 from being interfered with by electrical signals in the display or machine, a shielded electrode 770 is additionally disposed on a non-touch surface of the substrate 710 .
[0089] The above descriptions are merely preferred embodiments of the present invention, and are not intended to limit the scope of the invention. It is apparent to those of ordinary skill in the art that, modifications and variations can be made without departing from the spirit of the present invention, which should be covered in the protection scope of the present invention. | In the field of touch screens and more particularly capacitive touch screens, a digital capacitive touch screen is provided, which includes a touch substrate and a touch system circuit. The touch system circuit has a touch excitation source and a touch signal detection unit. At least two staggered electrode groups are disposed on the touch substrate, and multiple electrode lines of the electrode groups are connected to the touch excitation source. In a working period of the touch system circuit, for at least one moment, the touch excitation source applies touch signals to more than two electrode lines at the same time, and the touch signal detection unit detects the change of the touch signal on at least one of the electrode lines. Thereby, a high-definition and large-sized digital capacitive touch screen is obtained. The digital capacitive touch screen has a simple structure, low cost, and high reliability. | 6 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates in general to evacuated envelopes for receiving solar energy.
2. Description of the Prior Art
Many attempts have been made to provide apparatus for converting solar energy into either heat where it can be used or directly into electrical energy by using photovoltaic devices. Such devices when used in the earth's atmosphere, are subject to degradation due to environmental factors. Also, it is important that photovoltaic devices do not become overheated as "thermal runaway" will ultimately destroy the devices and their characteristics.
SUMMARY OF THE INVENTION
The present invention comprises a solar energy receiver having an evacuated transparent envelope such as glass in which is mounted a solar receiver that is formed of extruded metal as, for example, aluminum through which passages are formed and in which are mounted fluid conducting tubes which pass through the openings in the extrusion and which have been expanded so as to form tight metal bonds with the extrusion so as to provide high thermal conductivity between fluid in the tubes and the extrusion.
The present invention provides a controlled atmosphere such as vacuum or an inert gas enclosed in an envelope surrounding the solar energy receiver which comprises a high electrical conductivity heat sink such as an aluminum extrusion formed with a plurality of openings through which fluid conduits such as copper tubing is passed. The copper tubing is expanded by applying hydraulic pressure to expand it or by drawing a mechanical expander through the tube so as to force a mechanical bond by slightly working the tube and the aluminum receiver. Headers are attached to the copper tubes and fluid is passed through the receiver so as to prevent it from overheating and also to remove the thermal energy. In some embodiments, photovoltaic devices are mounted on the receiver so as to directly convert solar energy into electrical energy and the fluid is used to cool the device for maintaining thermal control. The solar receiver may be mounted in a high concentration ratio compound parabolic concentrator. The fluid passages pass through the glass envelope with suitable glass to metal seals.
Other objects, features and advantages of the invention will be readily apparent from the following description of certain preferred embodiments thereof, taken in conjunction with the accompanying drawings although variations and modifications may be effected without departing from the spirit and scope of the novel concepts of the disclosure and in which:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view illustrating a solar energy receiver according to a first embodiment of the invention;
FIG. 2 is a sectional view taken on line II--II in FIG. 1;
FIG. 3 is a partial sectional view taken on line III--III from FIG. 1;
FIG. 4 is an enlarged detail sectional view illustrating the method of mechanically bonding a copper tube to the aluminum receiver;
FIG. 5 illustrates a high concentration ratio compound parabolic concentrator with the receiver of the invention mounted therein;
FIG. 6 is a sectional view of a second embodiment of the invention; and
FIG. 7 is a sectional view taken on line VII--VII from FIG. 6.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 illustrates a first embodiment of a solar collector designated generally as 10 which comprises a glass envelope 11 in which is mounted a metal hollow extrusion 12 which is generally cylindrical in shape and has thin walls. Integrally formed openings are formed in portions 8, 9, 10 and 11 as shown in FIG. 2 in the internal surface of the aluminum cylinder 12 and fluid conduits as, for example, copper tubes 14, 22, 21 and 23 are received in the openings formed in portions 8, 9, 10 and 11. In order to provide a very tight mechanical bond between the copper tubing 14 and the extrusion 12 the tube 14 is expanded with a mechanical expander 16 as shown in FIG. 4 which is drawn with a rod 17 and a driving means 18 through the tube 14 such that the portion 14a after which it has passed through the tube is in tight intimate contact with the member 12. This tight contact assures that heat will flow in a very efficient manner from the member 12 through the tube 14 and into cooling fluid and heat removing fluid contained in the tube 14 in operation. Although a metal expander has been shown as the method of expanding the tube 14, it is to be realized, of course, that the tube can be expanded by applying hydraulic or fluid pressure to the tubes to expand them.
Headers are then attached to each end of the tubes 14, 22, 21 and 23. For example, the left end relative to FIG. 1 of tube 14 is connected by conduit 31 to the left end of tube 22 and the left end relative to FIG. 1 of tube 23 is connected by conduit 32 to tube 21. A header 33 is connected to tubes 14 and 23 as shown in FIG. 3 at the right end of FIG. 1 and a header 67 is connected to the tubes 21 and 22 at the right end of FIG. 1. A short conduit 60 is connected to the header 33 as shown in FIG. 3 and an expandable bellows 53 is connected to the tube 60 and the other side of the bellows 53 is connected to tube 51 which passes through an end cap 41 with a brazed seal 52. Header 67 is connected to short tube 65 which connects to expandable bellows 66 which connects to tube 61 and passes through end cap 41 with a brazed seal 62. The metal end cap 41 is connected to the glass envelope 11 with a Kovar or other glass to metal seal 70.
A spring positioning holder 44 is formed with flexible legs 45, 47, 46 and 48 and is engageable with the left end relative to FIG. 1 of the member 12 so as to position the member 12 within the envelope as shown. The assembly has the end support 44 placed over it before it is inserted into the glass enclosure 11 and after the seals 52, 62 and 70 are made, the glass enclosure 11 is drawn to a suitable vacuum as, for example, 10 31 4 to 10 -6 torr absolute vacuum through a pumping port 43 which is sealed after the gas has been removed. A suitable getter may be placed in the envelope prior to baking so as to obtain and maintain the ultimate vacuum.
The bellows 53 and 66 allow for thermal expansion in the envelope and adjust the length of the internal structure depending upon the temperature within the envelope.
FIGS. 5, 6 and 7 illustrate a modification of the invention wherein the heat receiver may be placed within a high concentration ratio compound parabolic concentrator 200 so that incoming solar energy will be concentrated on the receiver 100. In this embodiment the receiver carries a plurality of photovoltaic devices 123 which are mounted on a heat sink 103 that might be of aluminum or other suitable material and devices 123 are electrically connected together in a series and parallel arrangement so as to develop the desired voltage and current capacity. The photovoltaic devices are connected by leads 121 and 122 which pass through a Kovar or other glass to metal electrical feed through seal 119 which passes through the end 118 of the glass envelope 101. The aluminum extrusion 103 is formed with a plurality of openings into which metal tubes such as, for example, copper, and designated 104, 106, 107, 108 are placed and then the copper tubing is expanded either with a suitable expander as illustrated in FIG. 4 or by applying fluid pressure thereto to cause a tight seal between the tubes and the extrusion 103. Header 111 is connected between tubes 104 and 106 at the left end of FIG. 6 and header 112 between tubes 107 and 108 at the left end of FIG. 6. A vertical header 109 is connected between the opposite ends of tubes 104, 106 and tubes 107 and 108 such that fluid can pass through an input pipe 113 which extends through the glass envelope end 118 with a Kovar or other type of glass to metal seal and which then connects through the header 111 to allow fluid to pass through the tubes 104 and 106. At the right end relative to FIG. 6, the fluid passes from tubes 104 and 106 through the header 109 to the right ends of tubes 107 and 108 and the fluid then passes to the left relative to FIG. 6 and through the header 112 to an output conduit 114 which extends through the end 118 of the glass envelope 101 with a suitable glass to metal seal as, for example, the Kovar or other types of seals 116 and 177.
The receiver 100 is then mounted in the compound parabolic concentrator 200 as illustrated in FIG. 5 so that the incoming energy is received by the photovoltaic devices 123 and electrical energy is generated by the thermal energy. The extrusion 103 which is generally crescent shaped as illustrated in FIG. 7 is cooled so that it does not exceed the desired temperatures by the fluid passing through the various headers in the tubes 104, 106, 107 and 108 and due to the good thermal contact between the aluminum extruded member 103 and the copper tubes 104, 106, 107 and 108 the heat flow will be very efficient. The expansion of the tubes also prevents movement of the tubes relative to the extrusion.
The outer surface of the extrusion 103 upon which the photovoltaic devices 123 are mounted may be formed with faceted surfaces running parallel to the longitudinal axis on the outside of the semicircular element 103 which illustrates the thermal energy impinging upon the receiver 103.
It has been discovered that with a compound parabolic concentrator that the receiving area of the energy is not a cylinder but two very small segments of a cylinder. For a concentrator the concentration ratio C.R. is defined as the aperture width divided by the receiver circumference (length of surface capable of reradiation). The following chart gives examples of six models which have a design concentration ratio C.R. and actual concentration ratio C.R. The design C.R. determines the acceptance angle for the incoming energy and the truncated height is utilized to determine the actual aperture width and the resultant C.R. In the models a 1.5 inch diameter receiver was utilized.
______________________________________ TRUNCATION DESIGN HEIGHT ACTUALMODEL C.R. (INCHES) C.R.______________________________________1 10:1 20.9 5.342 20:1 31.9 7.053 10:1 10.2 3.894 10:1 7.0 3.285 20:1 10.4 4.166 20:1 7.1 3.47______________________________________
The major discovery is that the receiving surface is always above the horizontal axis for the assumed conditions. Because the design C.R. is very large, resulting in a relatively small acceptance angle, only incoming radiation which is normal to the aperture plane is assumed. That is, the collector is assumed to be a tracking system, remaining constantly in a position which gives essentially nothing but parallel rays of radiant energy impinging upon the aperture plane at an angle of 90 degrees (within the accuracy of the assumption that the sun's radiation angle is 0 degrees).
Models 1-6 indicate that the receiver design is critical to the C.R. chosen and the truncation height. For example, using Model 3 it can be seen that the receiving surface is not a cylinder, but two very small segments of a cylinder. Optimistically, the maximum angle subtended by the receiving surface is a maximum of 60 degrees on either side, or a total of 120 degrees receiving surface. Since the conventional definition of concentration ratio is the ratio of the aperture width to the circumference of the receiver, the arc length of the receiver surface is the denominator. If, from Model 5 the arc length of the receiving surface is used to define the C.R., since this arc length is only 1/3 that of the cylindrical receiver, the actual C.R. can be stated as being 11.66:1 instead of 3.89:1. The design C.R. was only 10:1 initially. Thus the design of the receiver is strongly affected by the selected C.R. for the initial design.
A coating for absorption of radient heat may be placed on the extrusions so as to increase the efficiency of the devices.
Although the invention has been described with respect to preferred embodiments, it is not to be so limited as changes and modifications can be made which are within the full intended scope of the invention as defined by the appended claims. | A solar energy receiver comprising an evacuated glass envelope in which is mounted an extruded aluminum energy receiving member through which fluid conducting tubes are inserted and then expanded so as to create a mechanical bond between the tubing and the aluminum extrusion to provide for good heat conductivity and wherein headers are connected to the fluid carrying conduits to supply fluid to and from the tubes. In one embodiment, photovoltaic devices are mounted on the extrusion and electrical energy is removed therefrom and the receiver is placed in an energy concentrator so as to derive the maximum available energy. | 8 |
RELATED APPLICATION
[0001] This application claims the benefit of U.S. Patent Application Ser. No. 60/941,065 filed May 31, 2007, which is incorporated by reference in its entirety.
BACKGROUND OF THE INVENTION
[0002] This invention relates to a disk refiner for ligno-cellulosic materials, and generally to disk refiners used for producing fiberboard and mechanical pulps for medium density fiberboard (MDF), thermomechanical pulps (TMP) and a variety of chemi-thermomechanical pulps (CTMP), which are collectively referred to as mechanical pulps and mechanical pulping process. In particular, this invention relates to steam flow through disk refiners in mechanical pulping processes.
[0003] A disk refiner may be used in a thermo-mechanical pulping (TMP) refiner in which the pulp material, such as wood chips, is ground in an environment of steam between a rotating grinding disk (rotor) and a stationary disk (stator) (or a pair of rotating disk rotors) each with radial grooves that provide the grinding surfaces. The rotor may operate at rotational speeds of 1000 to 2300 revolutions per minute (RPM).
[0004] Wood chips are fed to the center of the opposing disks of a disk refiner. The chips are broken down between the disks as centrifugal force pushes the chips towards the disk outer circumference. The refiner plates generally include a pattern of bars and grooves which provide repeated compression actions on the chips. The compression action results in the separation of lingo-cellulosic fibers out of the raw chips. The fiber separation transforms the raw chip material into fiber pulp suitable for a final product, such as fiberboards.
[0005] While the chips are retained between the disks, energy is transferred to the chips via the refiner plates attached to the disks. The energy is in the form of high centrifugal and compression forces applied to break-down the wood chips. The refining process also generates high frictional forces that causes water in the chip feed material to convert to high pressure steam.
[0006] In most disk refiners, the steam from the disk refiner flows in the same direction, e.g., radially outward from between the disks, as the fiber material exiting the refining disks. By way of example, typically between 60% and 100% of the steam produced between the disks in a refiner flows in a forward direction, which is the same direction as the fiber material moving between the refining disks. These percentages for forward flowing steam vary depending on refiner plate patterns and process conditions. After exiting the outer periphery of the fiber disks, the forward flowing steam carries fiber pulp through blow lines downstream of the disk refiner. The pressure of the forward flowing steam is released as the refined fiber pulp material exits the blow lines and enters bins and other relatively low pressure vessels. In MDF, the forward flowing steam typically adds little value to the pulping process and the pressure energy in the forward flowing steam is generally not used. In mechanical pulping, some systems allow for the recovery of heat energy in the forward flowing steam from a discharge cyclone, and other systems vent the forward flowing steam to atmosphere. When recovered such as via a heat exchanger, the heat from forward flowing steam from the mechanical refining processes is typically used for paper machine dryers and on pulp drying equipment
[0007] High pressure steam is needed in the feeding side of the refiner in MDF and other mechanical pulping systems. Steam is used to soften the wood to improve the performance of the refiner and produce fiber. High pressure steam for refining is usually provided a combination of back-flowing steam from the refiner and fresh steam, usually generated by a boiler. Fresh steam is expensive to produce in terms of energy consumption. There is a long felt need for sources of high pressure steam for pulping processes.
[0008] A source of high pressure steam is the steam generated during mechanical refining. High pressure steam is generated between refining disks in a disk refiner. In a traditional refiner, up to 40% of the high pressure steam generated between does not flow in a forward direction with the chip feed material. To the extent that the high pressure steam between the disks can be extracted without loss of pressure, the high pressure steam may be directed to a steaming vessel in a chip feed system of a mechanical refining plant.
[0009] A known technique to capture high pressure steam from the disks is to allow the steam to back flow against the movement of chip material between the refining disks and through the feeding system to the chip pre-steaming vessel. High pressure back flow steam has been used in the pre-steaming vessels. Separate piping has been added to refiners to allow back flow steam to bypass the conveyors and feeding devices from the feeding system, and allow the back flow steam to move with little resistance from the refiner inlet to the pre-steaming vessels.
[0010] The amount of back flow steam is generally reduced by the use of directional (low energy) refiner plates. Low energy plates typically reduce steam generation by 10 to 50% in a refiner and reduce the amount of back flow steam by 20 to 70%, as compared to conventional higher energy refiner plates. While directional MDF refiner plates are advantageous in reducing the energy required to drive a disk refiner, the reduction in the available back flow steam increases the amount of high pressure steam needed for a mechnical refining plant.
[0011] There is a long felt need for techniques to reduce the amount of high pressure steam needed to be produced at high energy costs for a mechanical refining plant. In particular, there is a long felt need to capture a greater amount of high pressure steam from the refining process than is presently captured using directional (low-energy) refiner plates in mechanical refining plants.
BRIEF DESCRIPTION OF THE INVENTION
[0012] A novel refiner plate has been developed to increase the amount of high pressure steam extracted from refiner plates, and especially low energy refiner plates. The refiner plate includes steam channels that cut through the refining section and provide a passage for back flow steam. Advantages of the refiner plate include increased amount of high pressure steam available for other purposes in the refining plant, and low-energy refining associated with directional plates.
[0013] A refining plate has been developed for refining lignocellulosic material, where the plate includes: a radially outer peripheral edge and a substrate surface; a refining zone including a plurality of substantially radially disposed bars and grooves between the bars, wherein the bars protrude upward from the substrate surface and the grooves each have a groove width, and a steam channel traversing the bars and grooves of the refining zone, wherein the steam channel has a radially outer end radially inward of the outer peripheral edge of the plate and a width substantially greater than the groove width.
[0014] The refining plate may include a dam extending across the steam channel at a radially outward inlet end of the channel. The plate, such as a rotor or stator plate, may include an inlet zone adjacent a radially inner end of the steam channel. The gap between bars in the inlet zone should be at least as wide as the steam channel. The refining plate comprise an annular array of plate segments where each segment includes the refining zone, and a plurality of the plate segments (but not necessarily all segments) includes at least one steam channel.
[0015] A method has been developed to extract high pressure steam from a refining system comprising: introducing a cellulose fibrous feed material to an inlet of a disk refiner; feeding the cellulose fibrous feed material between opposing disks of the refiner, wherein one disk rotates relative to the other; refining the cellulose fibrous feed material between opposing refiner plates each mounted on a respective one of the opposing plates, wherein each refiner plate has a zone of refining bars and grooves; back flowing steam generated during the refining of the feed material flows through channels in the zone of at least one of the plates, wherein the channels have a width substantially greater than a width of the grooves, and extracting the back flow steam from the disk refiner from an outlet radially inward of an outlet of the channels.
[0016] The pressure of the back flow steam may be extracted at a pressure of 1 to 8 bar (gauge pressure). The back flow steam is forced to flow radially inward through the channels (and possibly a discontinuous steam channel) by forming a radially outer end of the channel substantially radially inward of the outer circumference of the disks. The back flow steam may be discharged from the channel to a coarse zone of the refining plate, wherein the coarse zone is radially inward of the channel and spacing between the bars in the coarse zone is at least as wide as that of a steam flow channel.
BRIEF DESCRIPTION OF THE DRAWINGS
[0017] The following identified figures included with this application illustrate preferred embodiments and the best mode of the invention.
[0018] FIG. 1 is a front view of a first directional, low energy refiner plate segment wherein the segment includes a steam channel.
[0019] FIG. 2 is a side view of the first plate segment.
[0020] FIG. 3 is a front view of a second directional, low energy refiner plate segment, wherein the segment includes a steam channel.
[0021] FIG. 4 is a side view of the second plate segment.
[0022] FIG. 5 is a front view of a TMP refiner plate segment wherein the segment includes a steam channel.
[0023] FIG. 6 is a front view of a non-directional refiner plate segment wherein the segment includes a steam channel extending half-way through the refining zone.
[0024] FIGS. 7 and 8 are a front view and a side view, respectively, of a plate segment of a directional, low energy plate.
[0025] FIG. 9 is a schematic view of refiner system having an outlet for high pressure back flow steam.
DETAILED DESCRIPTION OF THE INVENTION
[0026] A steam channel has been developed for use in refiner plates, such as rotor and stator plates in mechanical pulping refining. The steam channel allows high pressure steam generated during mechanical refining of cellousic material, e.g., wood chips, to back flow through a refining zone(s) in the plates and be extracted as high pressure steam.
[0027] The refiner plate segments disclosed herein are primarily applicable to MDF and TMP refining and for use in a mechanical refiner, such as a disk refiner for refining wood fibers. The plate segments may be directional and low energy plates. Steam channels are included on the plate segments to increase the volume of high pressure steam that back flows through the refiner in a flow direction opposite to the flow of the chips flow between the plates of the refiner.
[0028] FIGS. 1 and 2 show a front view and a side view, respectively, of a stator or rotor plate segment 10 having an inlet section 12 and an outer section 14 . An array of plate segments is arranged in an annulus on a refiner disk to form an annular refining plate. The plate is mounted on a disk. In a disk refiner, a rotor plate faces a stationary stator plate with a refining gap between the plates. The plate is formed of plate segments 10 arranged in an annular array on the disk. The plate segments of a stator plate may have similar bar and groove features as an opposing rotor plates, or the stator and rotor plates may have different bar and groove features. The rotational direction for the rotor plate is typically counter-clockwise. The stator plate is typically stationary. A refining gap is defined between the opposing stator and rotor plates.
[0029] The inlet section 12 is the feeding part of the plate. The inlet section 12 feeds the incoming fibrous material to the outer refining section 14 , preferably with minimal frictional energy and minimal work of the feed material. The inlet section may include coarse bars that feed the chip material to the outer section. Between the coarse bars are wide gaps that allow for the passage of back flow steam.
[0030] The outer refining section 14 of the refiner plate segment is the area where the energy is applied to the feed material to break down the wood chips into a fibrous pulp. By way of example, the outer section should preferably be a radial distance of between 100 millimeters (mm) to 200 mm (4 to 5 inches).
[0031] By way of example, the outer refining section 14 may be comprised of straight bars 18 and narrow grooves 22 . A bar 18 is an extended ridge protruding from the substrate surface 19 of the plate segment. The height of the bar is typically at least as great as the width of the bar. The length of each bar is typically substantially greater than its width. The bars extend along their length in a direction predominately radial with respect to the plate segment, but the direction of the bar often also includes a tangential component, especially for directional, low energy refiner plates. The bars 18 may be straight, curved or irregular.
[0032] The bars may be grouped side-by-side in zones 20 of, for example, twenty (20) of parallel bars 18 . The bars are arranged so that they are relatively close to each other. The gap between adjacent bars defines a groove 22 . Each zone 20 of bars 18 typically includes an equal number of grooves 22 or one less groove than the number of bars. The refining zones 20 may span adjacent plate segments.
[0033] The grooves 22 each are defined by opposite sidewalls of adjacent bars 18 . The depth of the grooves extend from the upper region of the bars to the substrate surface of the plate. Typically, MDF plates have 3-5 mm bar widths, 5-12 mm groove widths, and 7-12 mm groove depths. TMP plates typically have 1.0-5.0 mm bar widths, 1.5-5.0 mm groove widths, and 1.8-8.0 mm groove depth (a really wide range.
[0034] Refining of the fibrous material generally occurs at the upper levels of the bars and grooves of the outer refining section 14 . The lower regions of the grooves, i.e., near the substrate 19 , typically serve to vent steam and allow chip feed and other materials flow radially outward through the refiner plate.
[0035] Pumping directional refiner plates typically have bars arranged such that frictional forces created during the crossing of rotor and stator plates contribute to a net forward force applied to the feed material. The bars are arranged at acute angles with respect to a radius and angle towards the rotational direction of the rotor plate. Directional plates reduce the retention time of the feed material between the plates. The refiner operates with a smaller operating gap between the rotor and stator plates/disks. Reducing the operating gap tends to reduce the amount of energy needed to achieve a given fiber quality.
[0036] Directional refiner plates also tend to generate less steam per amount of fiber produced due to the lower energy input. The pumping angles of the bars in directional refiner plates also tend to cause a greater percentage of the steam generated to flow forward (in the same radial direction as the chip material), as compared to bi-directional refiner plates having an average pumping angle of zero. The amount of backward flowing steam in directional refiner plates is significantly reduced as compared to bi-directional plates.
[0037] Running directional (or low-energy) refiner plates typically reduces steam generation by 30-50% and 10-20% in TMP, as compared to bi-directional plates. steam generation reduced 10-20% in TMP, 30-50% in MDF, usually. Back-flowing steam reduction with directional refiner plates may be 20 to 90%, as compared to bi-directional plates, with TMP plates have a lesser reduction in back-flow steam and MDF plates having a greater reduction in back-flow steam.
[0038] Dams 24 , 26 may be included in the grooves to retard the flow of fibrous materials in the lower region of the grooves. Dams 26 , 28 are arranged in the grooves to prevent excessive fiber flow through the grooves. Split height dams 26 may be arranged at radially inward regions of the grooves. Full height dams 28 (also referred to as “surface dams”) may be at the radially outward regions of the grooves or may be arranged throughout the length of the grooves. MDF and TMP refiner plate segments tend to have many dams arranged in their grooves. The dams increase the refining that occurs between the plates by slowing the flow of fibrous materials between the plates.
[0039] The dams between the grooves of refiner plates also substantially reduce the back-flow of steam. Steam may back flow by moving through the grooves generally radially inward and to the inlet to the refiner plates. Back flow steam flows radially inward and in a counter-flow direction to the generally radially outward movement of the chip and fiber material and much of the steam. The back flow steam occurs in the lower regions of the grooves, which regions are near the substrate of the plate. Back flow steam is most likely to occur in grooves that do not have dams. Dams block the flow of back flow steam.
[0040] The high pressure of back flow steam may be useful for other applications in a refiner plate. To promote back flow steam, channels 34 are preferably provided in the stator plate segment. The channels 34 provide a flow path to allow steam to back flow radially inward towards the center inlet of the refiner. The channels 34 provide passage for back flow steam through the refining zone. The steam channels facilitate the flow of steam in a counter-flow direction to a relatively large volume flow (as compared to the back flow steam) of fiber material being fed to the center inlet of the plates and moving radially outward to the outer circumferential outlet of the plates.
[0041] Steam channels 34 may be arranged in rotor plates. A rotor pumping effect (due to centrifugal force) may reduce the amount of back flow steam in a steam channel in a rotor plate. The pump effect also advantageously reduces the fiber flowing back in the rotor channels 34 , as compared to steam channels in a stator plate.
[0042] Stator steam channels have a higher efficiency for steam removal, but allow more fiber to flow back as compared to steam channels in a rotor plate. The steam channels 34 arranged in the stator plate segments because the centrifugal forces in the stator plate on steam flow in channels and grooves, is low compared to the centrifugal forces acting on steam flowing in the grooves on the rotating rotor plate.
[0043] The steam carrying channels 34 are preferably at least one-half inch wide (1.3 centimeter (cm)) and a length of two inches (5.1 cm) to eight inches (20.3 cm). The steam channel 34 may have a radially inward steam discharge end 36 adjacent, at or near the inlet section 12 of the stator plate segment. The radially inward end 36 of the channel preferably opens to a section in which the bars are spaced apart at least three-quarters of an inch (1.8 cm). The inlet section 12 of bars generally has bars space wide apart and allows for back flow of steam. A section of bars spaced apart at least three-quarters of an inch on a stator plate will allow steam to back flow through its grooves. Steam back flow channels may not be needed in zones of a refiner plate having bars spaced apart by at least three-quarters of an inch.
[0044] The radially outer end 38 of the steam channels 34 may not extend to the outer circumferential edge 40 of the plate segment. The outer end 38 of the channel may be one inch (2.54 cm) radially inward of the outer circumferential outer edge 40 of the plate. Alternatively, the outer end of the steam channel may be at approximately one-half the radial distance of the refining zone. The selection of the radial end location of the steam channel depends on the particular refiner and plates, the desired amount back flow steam and the refining process. Ending 38 the channel before the outer circumferential outer plate edge 40 prevents steam and chip material in the channel from flowing radially out the discharge of the plates. A surface dam may be placed at the radially outer end 38 of the steam channel, especially if the end is adjacent the plate edge 40 .
[0045] The channels 34 preferably span at least the inner radial half of the refining zone 14 and a much as 85% of the radial length of the refining zone 14 . Steam in the refining section of the refiner plate may back flow through the channel 34 to the center and/or inlet of the refiner.
[0046] The steam channels 34 are preferably at an acute angle with respect to a radial line of the stator plate. The channel angle may be in an opposite direction to the angle of the bars in the zone(s) adjacent the channel 34 . The channel angle may be 0 degrees to 60 degrees to a radial line. The angled channel reduces the tendency of chip material being push through the channel 34 in an opposite direction to the back flow steam. The chip material tends to flow over the channel in a direction generally transverse to the channel. The chip material tends not to flow in a direction parallel to the channel. The back flow steam in the stator channel 34 tends to flow in lower regions of the channel near the substrate and flow parallel to the channel. Accordingly, the chip material tends not to flow directly counter to the back flow steam in the channel 34 . However, the direction of the channel may be radial or in alignment with the angle of the bar.
[0047] The steam channels 34 may be as deep as the grooves between the bars. Alternatively, the channels may be shallower or deeper than the grooves depending on the construction of the refiner plate and the desired flow of back flow steam. In plates with multiple refining zones of bars and grooves, wide channels may separate the zones. The channels may be in a tangential direction if separating refining zones that are radially adjacent each other. The annular channels between refining zones may from a portion of a steam channel 34 . The steam channel may be discontinuous (see FIG. 3 ) along a radial direction of the plate, provided that there is a back flow steam path between the channel sections. Steam may flow between discontinuous channels by flowing in a direction generally perpendicular to a radius of the plate and between adjacent zones of bars and grooves.
[0048] More than one steam channel 34 may be used on each refiner plate segment. A steam channel need not be provided in every refiner plate segment in a plate array of segments. The geometry of the channel 34 may be selected based on a desired flow of back flow steam, the refining process, operating variables, and other features of the plate design. The steam channel(s) ay be straight, curved, zig-zagged and discontinuous.
[0049] FIGS. 3 and 4 are a front view and side view, respectively, of a refiner plate segment 42 having an outer refining section 44 , an inner refining section 46 , and a coarse bar feeding section 48 . A steam channel 50 extends partially through the outer refining section. The channel traverses the relatively narrow grooves 52 between finely spaced bars 54 in the outer refining section 44 . Surface dams 56 are in all grooves of the outer section. The radially inward refining section 46 has a steam channel 58 that is discontinuous with the channel 50 in the outer refining section 44 . Back flow steam moves from the outer channel 50 , through a channel gap 60 between the refining sections 44 , 46 and to the inner channel 58 . The steam back flowing through inner steam channel 58 discharges to the feeding section 48 that has wide space bars allowing the stem to back flow to a high pressure steam exhaust.
[0050] FIG. 5 is a front view of a plate segment 70 of a TMP stator plate. A steam channel 72 traverses an inner refiner zone 74 . The bars of the inner refiner zone are closely spaced as is typical. There is only a small acute angle between the bars and a radius, which is typical with TMP refining applications. The steam channel is straight and at an angle of approximately 45 degrees with respect to a radius, and at an opposite angle to the angle formed by the bars. The bars on opposite sides of the channel are sloped towards the channel. The bars adjacent the lower side of the channel have a steep slope 76 and the bars adjacent an outer side of the channel have a shallow slope 77 . The plate has an outer refining zone 78 without a steam channel. Steam generated in the inner refining zone 74 that flows into the channel may flow radially inward to a steam outlet near an inlet to the plate, which may be near a center of the plate.
[0051] FIG. 6 is a front view of a bi-directional plate segment 80 of a MDF stator plate. A wide steam channel 82 extends entirely through an inner refining zone 84 and partially through an outer refining zone 86 . The steam channel extends radially and is parallel to radially aligned bars of the inner and outer refining zones 84 , 86 . The steam channel 82 in the MDF bi-directional plate 80 allows steam generated in the refining zones 84 , 86 to flow radially inward to a high pressure steam exhaust port adjacent a radially inward position of the refiner plate.
[0052] The radial orientation of the bars allows the stator and corresponding rotor plate to be rotated clock-wise or counter-clock-wise during refining. In contrast to the bi-direction MDF plate shown in FIG. 6 , the MDF plates shown in FIGS. 1 and 3 are directional due to the angle formed by their bars with respect to a radial.
[0053] FIGS. 7 and 8 are a front view and a side view, respectively, of a plate segment 90 of a directional, low energy MDF stator plate. An inlet section 92 has wide gaps between the breaker bars that allow steam to flow radially inward. A refining section 94 includes discontinuous steam channels 96 , 98 and 100 .
[0054] The steam channels 96 , 98 , 100 form a zig-zag pattern traversing approximately two-thirds the radial length of the refining zone. The zig-zag pattern is formed by sections 96 , 98 of the steam channel that are generally perpendicular to the bars and a connecting steam channel section 100 generally parallel to bars. The zig-zag pattern tends to direct fiber in the channel to the bars of the refining zone 94 and allows steam to follow the zig-zag pattern. The zig-zag pattern reduces the fibers flowing with the back flowing steam to a high pressure outlet of the refiner.
[0055] The zig-zag steam channels 96 , 98 and 100 illustrates that a steam channel may traverse the plate along an angle opposite to the angle(s) formed by the bars of the refining section, and along an angle generally aligned with the bars of the plate. An opposite angled steam channel forms an angle with respect to a radial line that is on the opposite side of the radial line from the angle(s) formed by the refining section. An aligned steam channel forms an angle with respect to a radial line that is on the same side of the radial line as the angle(s) formed by the bars of the refining section.
[0056] As is evident from FIGS. 1 , 3 , 5 , 6 , and 7 , a steam channel may be straight or curved, continuous or discontinuous, form an angle opposite to the angles of the refining section or aligned with the refining section, and may be a combination of steam channel segments. Preferably, the steam channel is relatively wide (as compared to the groove widths in the refining section), does not extend to a radially outer edge of the plate or has one or more dams towards the outer edge to prevent steam venting out the outer periphery of the plate, and the channel is relatively deep to allow steam to flow radially inward and below the refining action at the bar tips.
[0057] FIG. 9 is a schematic side view of a thermomechanical (TMP) refiner system 60 , such as is described in US Patent Application Publication 2006/0006265, entitled “High Intensity Refiner Plate with Inner Fiberizing Zone.” A chip feed system 62 steams the wood chips and applies a pressure to the slurry of steamed wood chips. A steaming vessel 64 may be used to steam the chips at high pressure, wherein high pressure steam is introduced to the steaming vessel. The chip feed slurry may be at a high pressure, of for example 15 to 25 psig (pounds per square inch gauge).
[0058] The high pressure chip feed slurry is fed, via a high pressure chip feed tube 65 , to a high consistency primary refiner 66 that has relatively rotating disks. The disks are housed in a casing 68 of the primary refiner 66 . A pair of disk oppose each other in the casing such that the array of stator plates face the array of rotor plates and both arrays are coaxial. A narrow gap separates the bars of the stator plate and bars of the rotor plate. The casing is operated at a high pressure, e.g., 1 to 6 bar for TMP, and 6 to 8 bar to MDF. A refiner feed device 71 , such as a ribbon feeder, receives the high pressure chip feed slurry and delivers the pressurized slurry to a center inlet of one of the disk such that the slurry is fed between the disks at substantially the inner diameter of the disks.
[0059] A back flow steam path is formed by the channels and other steam flow passages on the refiner plates, e.g., the stator and/or rotor plate segments. Other steam flow passages may include inlet sections with widely spaced bars without dams, and annular gaps between inner and outer refining sections. The back flow steam discharges from the steam channels to the inlet sections where the spacing between the bars is relatively wide, e.g., at least one-half of an inch (1.2 cm). The wide grooves between the bars of the inlet section and/or the lack of dams in the inlet section allow back flow steam to flow to a high pressure steam exhaust 70 at the ribbon feeder 71 which is coupled to a center inlet of the disk refiner. Alternatively, piping for back flow steam may receive the steam from a coupling behind the chip chute 65 which is at the top inlet to the ribbon feeder 71 . Back flow steam may pass through the ribbon feeder, against the chip flow, and up the chip chute 65 to an inlet to the back flow steam pipe 72 .
[0060] The high pressure back flow steam exhausted from the disk refiner is available for use as high pressure steam in the preheating portion of the refining process. The back flow steam may be used to reduce the amount of fresh steam added to preheating. The use of high pressure back flow steam is conventional in TMP refining systems. The exhausted high pressure back flow steam may be introduced via steam line 72 to the steaming vessel 64 to steam wood chips prior to the refiner.
[0061] The refining plates with channels provide a relatively generous flow of high pressure back pressure steam. This high pressure back flow steam can be used in the refining plant instead of independently generated high pressure steam. The generous flow of high pressure steam provided by the steam channels of the refiner plate segments disclosed herein may reduce the energy requirements in a refiner plant by reducing the volume of high pressure steam to be independently generated.
[0062] While the invention has been described in connection with what is presently considered to be the most practical and preferred embodiment, it is to be understood that the invention is not to be limited to the disclosed embodiment, but on the contrary, is intended to cover various modifications and equivalent arrangements included within the spirit and scope of the appended claims. | A refining plate for refining lignocellulosic material including: a radially outer peripheral edge and a substrate surface; a refining zone having a plurality of substantially radially disposed bars and grooves between the bars, wherein the bars protrude upward from the substrate surface and the grooves each have a groove width, and a steam channel traversing the bars and grooves of the refining zone, wherein the steam channel has a radially outer end radially inward of the outer peripheral edge of the plate and the steam channel has a width substantially greater than the groove width. | 3 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of U.S. application Ser. No. 10/309,939 filed on Dec. 3, 2002, which is a continuation-in-part of U.S. application Ser. No. 09/970,008 filed on Sep. 27, 2001, now abandoned, which is a continuation of U.S. application Ser. No. 09/839,373 filed on Apr. 23, 2001, now abandoned, which claims priority from U.S. Provisional application Ser. No. 60/199,208 filed on Apr. 24, 2000. This application is also related to U.S. application Ser. No. 10/309,944, filed on Dec. 3, 2002. All of the above-identified applications are hereby incorporated by reference as if fully disclosed herein.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention of this application pertains to a method of packaging and shipping compressible structural panels, particularly ceiling panels or wall panels. In particular, the ceiling panels include an outer sheet and a connecting sheet which are spaced apart by spaced dividers. The dividers are compressible, yet resilient, allowing the thickness of the panel to be substantially reduced during packaging and shipping and further allowing the panel to regain its original dimensions after unpackaging. This reduction in volume during packaging and shipping can substantially reduce the packaging and shipping costs.
2. Description of the Prior Art
In the prior art, there is a plethora of structural panels for use as ceiling panels and wall panels. These structural panels have taken many forms, such as drywall or decorative or acoustic panels. However, these solid panels have virtually invariably been heavy and voluminous, thereby resulting in increased packaging and shipping costs. As the panels are typically shipped several times prior to installation—from the manufacturer to the wholesaler, from the wholesaler to the retailer, from the retailer to the installation site—the total shipping costs can be substantial.
OBJECTS AND SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide a method and apparatus for providing a structural panel which can be shipped at reduced expense.
It is therefore a further object of the present invention to provide a method and apparatus for providing a structural panel which has a reduced weight.
It is therefore a still further object of the present invention to provide a method and apparatus for providing a structural panel which has a reduced volume during shipping.
These and other objects are attained by providing a compressible structural panel which can be compressed prior to shipping in order to allow the panel to be shipped with reduced volume. The structural panel, upon being unpacked prior to installation, expands to regain its original shape and volume. Moreover, the compressible structural panel, whether in the compressed or uncompressed state, is very light as little material is used in order to achieve the compressibility.
In order to attain the low weight and the compressibility, along with the tendency to regain its original uncompressed configuration after unpackaging, the panels typically include an outer sheet of semi-rigid material with a plurality of dividers protruding from one face thereof. A connector in the form of a sheet or similar interconnecting system is secured to the distal edges of the dividers. The connector could take the form of a sheet or similar interconnecting system is secured to the distal edges of the dividers. The connectors could take the form of another sheet of material, strands of connective fibers, or the like.
The dividers are compressible in nature and could take numerous forms. In some embodiments, the dividers are elongated cells having foldable sides so that lateral or transverse pressure will compress the cells, and hence the divider, into a shallow space. The dividers can be formed from folding a strip of semi-rigid material such that the longitudinal sides or partitions fold inwardly or outwardly when the divider is compressed laterally. The dividers are constructed so as to normally assume an expanded or extended configuration and are resilient so as to return to that configuration after the compressed force has been removed.
A panel formed in accordance with the present disclosure for use in the packaging and shipping method will assume an expanded configuration in its normal at-rest configuration. However, when pressure with a perpendicular component is applied to the outer sheet or the connector, the dividers are compressed thereby allowing the entire panel to assume a very thin thickness or profile. When the structural panel is being compressed, there typically should be very little, if any, sliding movement between the outer and connector sheets. This is advantageous for shipping purposes as a greater number of panels can be packaged in a container than is possible with prior art panels that have a uniform thickness during shipping and use. The panels, particularly in the uncompressed state, are predominantly air filled and, therefore, are very lightweight.
In particular, the present invention involves packaging the panels in a compressed configuration prior to shipping, and allowing the panels to regain their original shape upon unpackaging, typically after shipping and immediately prior to installation.
BRIEF DESCRIPTION OF THE DRAWINGS
Further objects and advantages will become apparent from the following description and claims, and from the accompanying drawings, wherein:
FIG. 1 is an isometric view of a panel formed in accordance with the present disclosure for use with the packaging and shipping method of the present invention.
FIG. 2 is a fragmentary isometric view looking upwardly at a drop ceiling in a building structure, with the panels of FIG. 1 incorporated therein.
FIG. 3 is an enlarged fragmentary section taken along line 3 — 3 of FIG. 2 .
FIG. 4 is a front elevation of a strip of material from which a divider of the panel is made.
FIG. 5 is a front elevation of the strip of material shown in FIG. 4 being creased to form pre-fold lines.
FIG. 6 is a front elevation of the strip of material shown in FIG. 4 after having been creased as shown in FIG. 5 .
FIG. 7 is a front elevation of the strip of material shown in FIG. 6 having been folded along the preformed fold lines.
FIG. 8 is a front elevation of the divider as shown in FIG. 7 having been compressed.
FIG. 8A is an enlarged section of the circled area of FIG. 8 .
FIG. 9 is a front elevation similar to FIG. 8 with a layer of adhesive shown in dashed lines positioned above and below the divider.
FIG. 10 is a front elevation similar to FIG. 9 with an outer sheet and a connector sheet being positioned above and below the layers of adhesive.
FIG. 11 is a front elevation showing the composite illustrated in FIG. 10 being heat compressed between heating elements.
FIG. 12 is a fragmentary end elevation of a panel formed in accordance with the present disclosure for use with the packaging and shipping method of the present invention and with a decorative layer of material being adhesively secured to the outer sheet of the panel.
FIG. 13 is a fragmentary end elevation of the panel as shown in FIG. 12 being compressed between heated press elements.
FIG. 14 is an end elevation of a panel as shown in FIG. 12 having dividers with asymmetric partitions and with the panel fully expanded.
FIG. 15 is an end elevation similar to FIG. 14 with the panel being partially compressed.
FIG. 16 is an end elevation similar to FIG. 15 with the panel being slightly further compressed.
FIG. 17 is an end elevation similar to FIG. 16 with the panel being fully compressed.
FIG. 18 is an isometric view of the panel as shown in FIG. 14 .
FIG. 19 is an enlarged isometric view of a portion of the panel shown in FIG. 18 .
FIG. 20 is an isometric view of the panel shown in FIG. 18 in a fully compressed condition.
FIG. 21 is an enlarged isometric view of a portion of the panel as seen in FIG. 20 .
FIG. 22 is an isometric view of a plurality of panels stacked together while in a compressed condition.
FIG. 23 is an isometric view of the panels shown in FIG. 22 in an expanded condition.
FIG. 24 is an enlarged fragmentary end elevation of the panel shown in FIG. 14 with end supports for the panel to inhibit the panel from bending.
FIG. 25 is a fragmentary section taken along line 25 — 25 of FIG. 24 .
FIG. 26 is a fragmentary isometric with parts removed showing an end support on one end of the panel and a second end support being installed on the opposite end of the panel.
FIG. 27 is a fragmentary vertical section taken through a portion of the panel illustrating an alternative embodiment of the divider wherein the divider includes an inner layer of a metallic foil.
FIG. 28 is a fragmentary vertical section taken through the panel similar to FIG. 27 showing still another alternative arrangement of the divider wherein a metal foil is applied to the outer surface of the divider.
FIG. 29 is a transverse section taken through the panel as shown in FIG. 14 with the panel being compressed on its top surface.
FIG. 30 is a section taken along line 30 — 30 of FIG. 29 .
FIG. 31 is an end elevation of the panel shown in FIG. 14 with the panel being curved concave upwardly.
FIG. 32 is an end elevation of a panel in accordance with a second embodiment of the panel wherein the partitions of the dividers are symmetric rather than asymmetric as shown in FIG. 31 .
FIG. 33 is an isometric view showing a panel in accordance with the present disclosure for use with the packaging and shipping method of the present invention wherein the connection means are elongated strands or fibers that are secured to the dividers distally from the outer sheet.
FIG. 34 is an enlarged isometric showing a portion of the panel illustrated in FIG. 33 .
FIG. 35 is an isometric view of the panel shown in FIG. 33 with the panel having been bent or curved so as to be upwardly concave.
FIG. 36 is an end elevation of a panel formed in accordance with the present disclosure for use with the packaging and shipping method of the present invention and corresponding to the panel shown in FIG. 32 .
FIG. 37 is an end elevation of the panel shown in FIG. 36 with the panel partially compressed.
FIG. 38 is an end elevation of the panel shown in FIG. 37 having been fully compressed.
FIG. 39 is an isometric view of the panel shown in FIG. 38 in a fully compressed condition.
FIG. 40 is an isometric view of a portion of the panel shown in FIG. 36 in a fully expanded condition.
FIG. 41 is an isometric view of a plurality of panels of the type shown in FIG. 36 having been compressed and stacked together.
FIG. 42 is an isometric view of a portion of the panels of the type shown in FIG. 36 having been stacked in a fully expanded condition.
FIG. 43 is a diagrammatic end elevation of a panel with asymmetric dividers illustrating dimensional characteristics thereof.
FIG. 44 is a diagrammatic end elevation of a panel with symmetric dividers illustrating dimensional characteristics thereof.
FIG. 45 is an enlarged end elevation of a portion of the panel of FIG. 43 illustrating other dimensional characteristics.
FIG. 46 is an enlarged end elevation of a portion of the panel of FIG. 44 illustrating other dimensional characteristics.
FIG. 47 is an end elevation similar to FIG. 45 showing the panel compressed with a force F.
FIG. 48 is an end elevation similar to FIG. 46 showing the panel compressed with a force F.
FIG. 49 is an isometric view of another embodiment of a divider for use in the panel of the present disclosure for use with the packaging and shipping method of the present invention.
FIG. 50 is an end elevation of the divider shown in FIG. 49 .
FIG. 51 is an end elevation of a panel including a plurality of the dividers shown in FIG. 49 in an expanded form.
FIG. 52 is a reduced end elevation of the panel shown in FIG. 51 in a compressed form.
FIG. 53 is an isometric view of still another embodiment of a divider for use in the panel of the present disclosure for use with the packaging and shipping method of the present invention.
FIG. 54 is an end elevation of the divider shown in FIG. 53 .
FIG. 55 is an end elevation of a panel formed in accordance with the present disclosure for use with the packaging and shipping method of the present invention and utilizing the divider of FIG. 53 with the panel in an expanded form.
FIG. 56 is a reduced end elevation of the panel of FIG. 55 in a compressed form.
FIG. 57 is an isometric view of still another embodiment for a divider for use in the panel of the present disclosure for use with the packaging and shipping method of the present invention.
FIG. 58 is an end elevation of the divider shown in FIG. 57 .
FIG. 59 is an end elevation of a panel utilizing the divider of FIG. 57 with the panel shown in an expanded form.
FIG. 60 is a reduced end elevation of the panel shown in FIG. 59 in a compressed form.
FIG. 61 is an isometric view of still another divider for use in the panel of the present disclosure for use with the packaging and shipping method of the present invention.
FIG. 62 is an end elevation of the divider shown in FIG. 61 .
FIG. 63 is an end elevation of a panel utilizing the divider shown in FIG. 61 and with the panel in an expanded form.
FIG. 64 is a reduced end elevation of the panel shown in FIG. 63 in a compressed form.
FIG. 65 is an exploded isometric view of a panel similar to that shown in FIG. 1 that has been rigidified by providing additional dividers at the ends of the panel that extend perpendicular to the primary dividers.
FIG. 66 is a side elevation of the panel shown in FIG. 65 .
FIG. 67 is an end elevation of the panel shown in FIG. 65 .
FIG. 68 is an end elevation of a further embodiment of the present disclosure for use with the packaging and shipping method of the present invention in which the panel can be bent at a right angle.
FIG. 69 is an isometric view of a panel formed as in FIG. 68 with the panel in a fully compressed condition.
FIG. 70 is a side elevation of the panel shown in FIG. 69 .
FIG. 71 is an end elevation similar to FIG. 68 with the panel slightly further expanded.
FIG. 72 is an isometric view of the panel of FIG. 68 having been bent along a right angle and with the panel fully expanded.
FIG. 73 is an end elevation of the panel as shown in FIG. 72 .
FIG. 74 is an fragmentary isometric view of an end of a panel with a segment of the panel having been partially cut.
FIG. 75 is a fragmentary isometric similar to FIG. 74 with the partially cut segment of the panel having been compressed and positioned for receipt of an elongated clip.
FIG. 76 is a fragmentary isometric similar to FIGS. 74 and 75 showing the clip having been mounted on the compressed segment of the panel.
FIG. 77 is a fragmentary isometric similar to FIG. 76 wherein the clip mounted on the compressed segment of the panel is being folded upwardly.
FIG. 78 is a fragmentary isometric similar to FIG. 77 wherein the clip mounted on the compressed segment of the panel has been folded 900 into abutment with the new end of the panel.
FIG. 79 is an enlarged fragmentary section taken along line 79 — 79 of FIG. 78 .
FIG. 80 is a fragmentary isometric view of an alternative arrangement of a ceiling system wherein panels are suspended from rather than supported by a supporting gridwork.
FIG. 81 is an isometric view of a panel for use in the ceiling system shown in FIG. 80 .
FIG. 82 is a fragmentary isometric view of an end of a clip member used in the panel of FIG. 81 .
FIG. 83 is a fragmentary isometric view of the clip of FIG. 82 mounted on the longitudinal end of the panel shown in FIG. 81 .
FIG. 84 is an enlarged fragmentary longitudinal section taken along line 84 — 84 of FIG. 80 .
FIG. 85 is an enlarged fragmentary sectional taken along line 85 — 85 of FIG. 80 .
FIG. 86 is a fragmentary vertical section similar to FIG. 85 with the conventional acoustical tiles removed from their supported relationship to the support members.
FIG. 87 is a fragmentary transverse vertical section taken through the panel of FIG. 81 showing the outer sheet extended from a longitudinal side edge of the panel.
FIG. 88 is a fragmentary vertical section similar to FIG. 87 with the extended outer sheet being folded up and adhesively secured to a longitudinal end of the panel of FIG. 81 .
FIG. 89 is a fragmentary vertical section similar to FIG. 88 with the panel slightly compressed.
FIG. 90 is a fragmentary vertical section similar to FIG. 89 with the panel further compressed.
FIG. 91 is a fragmentary vertical section similar to FIG. 90 with the panel substantially fully compressed.
FIG. 92 is a fragmentary longitudinal vertical section showing the outer sheet extending longitudinally from one end of the panel of FIG. 81 .
FIG. 93 is a longitudinal fragmentary vertical section similar to FIG. 92 with a stiffener strip supported on the outer sheet extension.
FIG. 94 is a longitudinal fragmentary vertical section similar to FIG. 93 with a clip secured to the outer sheet extension.
FIG. 95 is a longitudinal fragmentary vertical section similar to FIG. 94 with the clip being folded upwardly to overlie the longitudinal end of the panel.
FIGS. 92A–95A are views identical to FIGS. 92–95 , respectively, showing an alternative system for mounting a clip to the end of a panel with the end of the panel being compressed in a manner to replace the stiffener strip used in FIGS. 92–95 .
FIG. 96 is an enlarged fragmentary transverse vertical section taken along line 96 — 96 of FIG. 81 .
FIG. 97 is a transverse section with portions removed showing one divider being removed to facilitate a folding of the panel.
FIG. 98 is a transverse section with portions removed similar to FIG. 97 showing the panel folded about the space where the divider was removed as seen in FIG. 97 .
FIG. 99 is a fragmentary section taken through an alternative embodiment of a compressed panel showing a unique system for gluing the cellular structures to the outer and cover sheets.
FIG. 100 is a fragmentary section similar to FIG. 99 with the panel fully expanded.
FIG. 101 is a fragmentary isometric showing an alternative clip embodiment connected to the end of a panel.
FIG. 102 is an enlarged fragmentary section taken along line 102 — 102 of FIG. 101 .
FIG. 103 is a fragmentary isometric showing the clip being moved into a closed position at the end of the associated panel.
FIG. 104 is a fragmentary vertical section showing a panel with a clip of the type shown in FIG. 103 supporting adjacent panels from an inverted T-grid support system.
FIG. 105–107 are fragmentary vertical sections showing sequential steps for mounting the panel with a clip of the type shown in FIG. 101 to an inverted T-grid support system.
FIG. 108 is a fragmentary vertical section with parts removed illustrating a U-shaped support system and panels with side edge clips for cooperation therewith.
FIG. 109 is a fragmentary vertical section similar to FIG. 108 showing a deeper U-shaped support system.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
At the outset, the panels disclosed herein are disclosed in the parent application, Ser. No. 10/309,939 filed on Dec. 3, 2002, the contents of which have been incorporated herein by reference.
Referring now to the drawings in detail wherein like numerals refer to like elements throughout the several views, one sees that FIGS. 1 and 12 show a typical compressible structural panel 50 which may be used with the invention of the present method. Compressible panel 50 includes a plurality of compressible parallel dividers or beams 52 extending between an outer sheet 54 (see FIG. 12 ) and a connector sheet 56 . A decorative sheet may be provided to overlie the outer sheet 54 . Compressible structural panel 50 is compressible from its normal expanded condition shown in FIGS. 1 and 12 to a fully compressed condition as shown in FIG. 17 . Particularly in its normal expanded state, the panel is comprised mostly of air and is, therefore, very light and easy to handle.
FIGS. 22 and 23 illustrate the method of the present invention. Firstly, a stack of uncompressed panels 50 is provided as shown in FIG. 23 . Then, pressure or some similar method is used to compress the stack of panels 50 to the configuration shown in FIG. 22 . Then, a package 1000 is formed around the stack of compressed panels 50 by methods that would be known to those skilled in the art after review of the present disclosure. Package 1000 is then shipped. A plurality of these packages can be shipped from a manufacturer to a wholesaler. The wholesaler can then send a portion of the plurality of packages to any number of retailers. The retailers can then further divide the received packages into smaller groups of packages and send these smaller groups of packages to any number of customers, typically at a site of installation. Alternatively, with the increased ease of packaging and shipping these packages, a wholesaler may even ship directly to the retail sites or points of installation, particularly after receiving an order from an electronic system, such as the internet, by accessing a website or receiving an e-mail. After the packages are received, the packaging is removed so that panels 50 can reach the expanded configuration, either by way of natural resilience or by way or the application of heat, as described herein.
The panel 50 has many possible embodiments, examples of which will be described hereinafter. Further, these embodiments can take many forms, such as a wall panel, a fixed ceiling panel, or panels for a drop ceiling such as shown in FIGS. 2 and 3 wherein a gridwork of elongated inverted T-shaped support members 60 are conventionally supported from a ceiling thereby defining rectangular openings 62 and peripheral support edges 64 around those openings on which a ceiling tile or panel 50 can be positioned.
As shown in FIG. 12 , dividers 52 are formed from the individual strips of material shown in FIG. 4 which have been pre-creased and folded into a desired configuration so that when incorporated into the panel 50 are transversely compressible allowing the panels to be compressed for packaging and shipping. Outer sheet 54 , connector sheet 56 and dividers 52 may be made from the same or different materials, and are typically held together by adhesive 68 .
The dividers 52 , shown in cross section in FIG. 12 , might be formed from a continuous strip of material but in the disclosed embodiment are each individual dividers of an elongated cellular or tubular configuration.
FIG. 4 illustrates the flat strip 66 before being passed into the creaser of FIG. 5 . In the crease, the material is passed between rotary creasing wheels 70 and back up rollers 72 so that longitudinally extending creases 74 (including 74 a , 74 b , 74 c as shown in FIG. 6 ) are formed in the material at predetermined laterally spaced locations. Strip 66 is then folded into the configurations illustrated in FIGS. 7 , 8 and 8 A. As shown in FIG. 7 , typically lower triangle 78 has a broader base than the upper triangle 80 . Applying pressure to the cell as configured in FIG. 7 in a vertical direction causes the components of the cell to compress so that the divider assumes the compressed configuration as shown in FIG. 8 . Typically, adhesive 68 is applied when the cell is in the compressed configuration.
As shown in FIG. 10 , the divider 52 with adhesive 68 applied to its upper and lower faces is passed between the outer sheet 54 and the connector sheet as shown in FIG. 11 , the entire laminate is then compressed between heated plates 82 which activate the adhesive 68 in the case of thermoplastic adhesives or act as a catalyst in the case of thermosetting adhesives.
If a thermosetting resin is used in bonding the glass fibers within the strips 66 and sheets 54 and 56 of material, the panel will naturally expand to its preformed condition, as shown in FIG. 12 , after having been compressed and bonded together. If a thermoplastic resin is used, it will remain compressed but need only be reheated and the strips will inherently expand under the heat. The panel can either inherently expand or be selectively expanded to a desired height or thickness.
As shown in FIG. 13 , the decorative sheet 58 could also be positioned between the outer sheet 54 and the heat press 82 with a suitable adhesive therebetween the bond the decorative sheet to the outer sheet thereby resulting in the panel illustrated in FIG. 12 .
FIGS. 14–17 illustrate the assembled panel in progressively compressed configurations.
A problem with conventional ceiling panels of the prior art is that they remain the same size and thickness during shipment, installation and use. However, with the present invention, the panels are compressed for shipping purposes so that far more panels can be packed in one container for shipping purposes thereby substantially reducing the volume shipped thereby substantially reducing shipping costs. Moreover, the light weight design of the panels described herein substantially reduces the shipping weight. Upon unpackaging, typically immediately prior to installation, the panels 50 can be allowed to naturally regain their original configuration or in some embodiments, as described hereinabove, a heater can be used to vary the thickness of the final panel.
As shown in FIG. 31 , panel 50 can be easily flexed or bent transversely of the direction in which the elongated dividers 52 extend to facilitate the insertion of the panel into the support structure of a drop ceiling. However, as illustrated in FIGS. 24 and 25 , panel 50 can be made substantially more rigid by placing support members 84 at opposite ends of the panel so as to cover the open ends 86 of the tubular or cellular dividers. Support members 84 can be preformed C-shaped channel members 88 as shown in FIGS. 24 and 25 or strips 90 of adhesive material as shown in FIG. 26 . Similarly, as shown in FIGS. 65–67 , a divider 52 a could be placed at each end of the panel to cover the open ends of the parallel dividers 52 . The outer sheet 54 and connector sheet 56 are extended to cover the dividers 52 which serve to make the panel 50 more rigid in the cross-direction.
The structural characteristics of divider 52 can be varied by laminating the inner or outer surface of the divider with another sheet of material and possibly a metallic sheet material 92 , as shown in FIGS. 28 and 27 , respectively.
As shown in FIGS. 29 and 30 , pressure applied to one side of the panel 50 will not deform the opposite of the panel 50 .
FIGS. 33–35 illustrate a second embodiment of a panel 94 wherein the connector sheet 54 has been replaced with a connector in the form of a plurality of elongated flexible but non-extensible strands or fibers 96 .
In both FIGS. 12 and 34 , the disclosed panels have dividers which have longitudinal fold lines 100 wherein the side partitions fold inwardly when the panel is compressed. The side partitions thereby define upper and lower portions 98 a and 98 b which are rectangular but wherein the upper portion 98 a is of a smaller dimension than the lower portion 98 b . This may be considered an asymmetric configuration.
FIGS. 36–42 illustrate a third embodiment which is identical to that shown in FIG. 12 except that the partitions 104 in the dividers 105 are symmetric in configuration. In other words, fold lines 106 along the partitions 104 are positioned so that an upper rectangular portion 104 a of each partition is of equal size to a lower rectangular portion 104 b . The compressed and expanded forms of the panel 102 shown in FIGS. 36–38 are illustrated isometrically in FIGS. 39 and 40 . FIGS. 41 and 42 illustrate the stacking of the compressed panels 102 for shipping.
FIGS. 49–52 illustrate an alternative embodiment wherein the connector sheet is eliminated by use of a divider 110 which is hourglass-shaped.
FIGS. 53–56 illustrate a further alternative embodiment of panel 132 wherein dividers 134 are not cellular in and of themselves but are rather strips of material that have been folded into a zig-zag pattern and secured between an outer sheet and a connector sheet 138 thereby forming a cellular compressible panel.
FIGS. 57–60 illustrate yet another embodiment of divider 152 for use in panel 154 . This divider 152 includes a pair of parallel outer crease lines 156 with folds in the same direction therein spaced inwardly from the side edges 158 of a strip of material from which the divider is formed and a third intermediate crease line 160 between the parallel outer crease lines. An upper marginal zone 162 is defined between one edge of the strip of material and one of the outer crease lines and a second much larger lower marginal zone is defined along the bottom of the divider between the associated edge of the strip of material and the adjacent crease line. The overlapping lower marginal zones are secured to each other thereby forming an integrated segmented outer sheet 168 formed from the plurality of lower marginal zones of the respective dividers.
A similar embodiment 170 of a divider is shown in FIGS. 61–64 where a strip of material is provided with a pair of outer crease lines 172 and an intermediate crease line 174 therebetween, with upper and lower marginal zones 176 and 178 being defined between the edges 180 of the strip and the outer crease lines 172 . The folds at the outer crease lines 172 are in an opposite direction to the fold along the intermediate crease line 174 so that the outer and lower marginal zones both project horizontally to the right, as viewed in FIG. 62 . Both of the horizontal zones extend horizontally beyond the intermediate crease line 174 and are adapted to overlap the upper and lower marginal zones of adjacent dividers to the right so that they can be secured thereto in any suitable manner to form the panel shown expanded in FIG. 63 and compressed in FIG. 64 .
A further embodiment of a panel 182 is disclosed in FIGS. 68–73 wherein the panel has an outer sheet 54 , a connector sheet 56 and a plurality of dividers 184 extending therebetween. As shown in FIGS. 68 and 71 , the dividers 184 a in a part of the panel are of Z-shaped cross-section while the dividers 184 b in the other part of the panel are of reverse Z-shaped cross-section. At the location 186 at which the direction of the dividers changes, the panel can be bent at a right angle as seen in FIGS. 72 and 73 so that the panel can, for example, follow the right-angled contours of building components on which it is mounted.
As shown in FIGS. 68 and 71 , the dividers 184 a in the right-hand portion of the panel are Z-shaped in cross-section so as to define an upper horizontal leg 188 that extends to the left, a lower horizontal leg 190 that extends to the right and a diagonal connecting leg 192 that connects the right edge of the upper leg to the left edge of the lower leg. The Z-shaped dividers 184 a are formed similarly to those described previously by placing crease lines in strips of material from which the dividers are made and then folding the strips of material along the crease lines.
As shown in FIGS. 68 and 71 – 73 , at the location 186 where the direction of the dividers changes, (in the illustrated panel, near its center) the panel can be folded at a right angle. The panel can then be fully expanded as shown in FIGS. 72 and 73 so that the legs of the dividers are perpendicular to each other thereby forming rectangular cells.
As shown in FIGS. 68 and 69 , it will be appreciated that the panel can also be compressed as with the earlier described embodiments of panels made in accordance with the present disclosure for use with the packaging and shipping method of the present invention.
In still a further embodiment 190 of the panel of the present disclosure for use with the packaging and shipping method of the present invention shown in FIGS. 99 and 100 , the dividers 192 are of the configuration illustrated for example in FIGS. 7–9 even though they have been inverted so that the bottom of the divider is shown on the top and secured to the overlying outer sheet 194 along three parallel glue lines 196 . The opposite side of the divider which is open and defined by two flaps 198 and 200 has one of the flaps 198 secured to the connector sheet 202 while the other flap 200 is unsecured. The panel 190 is shown in a compressed condition in FIG. 99 and an expanded position in FIG. 100 . In the compressed condition, it will be seen that the connector sheet 202 is shifted slightly to the right relative to the outer sheet 194 . When the panel is allowed to fully expand as shown in FIG. 100 , the left sidewall 204 of each cell folds out into a vertical orientation as the material from which the cell is made biases the sheet toward a flat orientation and in doing so, the connector sheet 202 is pulled or shifted to the left so that its edges become aligned with the edge of the outer sheet. The movement of the connector sheet to the left is caused by the unfolding of the sidewalls of the divider. The connection of the left flap 198 to the connector sheet 202 pulls the connector sheet to the left upon expansion of the cell. On the other hand, as the right side of the dividers unfolds and assumes a vertical orientation, the bottom flap 200 associated therewith is allowed to slide relative to the connector sheet 202 so that the flaps become more separated than they are in the compressed condition of FIG. 99 . The right sidewall of one divider is then folded into contiguous relationship with the left sidewall of an adjacent divider so that the sidewalls of the dividers reinforce each other and become somewhat rigid to rigidify the panel so that it cannot be easily compressed.
The compressible panel used is the method packaging and shipping of the present invention is also amenable to rigidification in a cross-direction in a manner illustrated in FIGS. 74–79 . A segment of the panel near an end thereof can be partially cut at 89 by cutting through the connector sheet 56 and the dividers 52 (in a direction transverse to the length of the dividers) but not severing the outer sheet 54 . This cut forms a small band 91 of material, which can be independently compressed as illustrated in FIG. 75 to receive a rigidifying clip 93 . The rigidifying clip in the disclosed embodiment is of substantially J-shaped cross-section having a long side 95 , a spaced parallel short side 97 , a connecting wall 99 interconnecting corresponding edges of the long and short sides and a lip 101 depending from the long side along the opposite edge from the connecting wall 99 . The clip is mounted on the compressed band of material so as to retain the material in a compressed state. The clip and compressed material can then be folded upwardly as shown in FIGS. 77 and 78 to form a rigidification along the end of the panel. The rigidified band of material can be adhesively secured in position after it has been folded upwardly as illustrated in FIGS. 78 and 79 if desired.
A panel 200 that has been modified to be suspendable from or supportable by the T-shaped support members 60 is shown in FIGS. 80–96 with a plurality of the panels shown in FIG. 8 installed in underlying relationship to existing acoustical panels 202 supported on support members 60 . As will be appreciated, each panel 200 is of the general type previously described and as seen in FIGS. 84–86 has an outer sheet 204 , a connector sheet 206 , and a plurality of parallel cellular dividers 208 therebetween. The cellular dividers are preferably, as previously described, compressible in nature and best seen in FIGS. 87–91 as being formed from individual strips of material that have been creased and folded so as to define elongated tubes having two truncated triangular areas 210 and 212 superimposed upon each other. The dividers 208 have foldable intermediate side walls 214 with fold lines 216 , which allow the side walls to either fold inwardly as shown in FIGS. 89–91 or fold outwardly as shown in FIGS. 87 and 88 depending upon a number of conditions including the type of binder used in the fiberglass matting material from which the dividers are made and the treatment of the dividers to heat and cold which will be described in more detail later.
At each end of the panel 200 along the open ends of the cellular dividers 208 , a unique clip 218 as seen best in FIGS. 81–86 , is secured to the panel. The clips are elongated and preferably extruded members of a rigid material such as aluminum, plastic, or the like and are generally of inverted J-shaped configuration as probably best seen in FIG. 82 . They therefore define a vertical main flat body 220 with a lower protruding lip 222 from the bottom edge of the main body. An upper downwardly opening hook-shaped channel 224 extends from the upper edge of the main body. Also along the upper edge is formed a second or horizontally opening hook-shaped channel 226 which protrudes from the main body in the opposite direction as the lip 222 even though it opens in the same direction as the lip 222 . An obliquely protruding rib 228 extends downwardly from the upper edge-of the main body beneath the horizontally opening channel 226 .
As shown in FIGS. 92–95 , the clip 218 is secured to the end of the panel 200 either by notching the end of the panel, as described previously, so that the outer sheet 204 protrudes longitudinally from opposite ends of the panel or the outer sheet can be made slightly longer and wider than the remainder of the panel so that it naturally protrudes from opposite ends and opposite sides as shown in FIGS. 87 and 92 defining outer sheet longitudinal extensions 230 and outer sheet lateral extensions 232 . An elongated straight stiffening strip 234 , which might be made of plastic, aluminum, paperboard, or the like, is adhesively bonded to the top surface of the outer sheet longitudinal extension 230 where it protrudes from the ends of the panel and clips are thereafter positioned over the outer sheet longitudinal extensions and the stiffeners as shown in FIG. 94 by inserting the stiffener strips and outer sheet longitudinal extensions into the downwardly opening J-shaped channels 224 adjacent to the main bodies with the lip 222 hanging over the innermost edge of the stiffeners. With the clips so positioned, the outer sheet longitudinal extensions 230 , stiffener 234 and clip 218 can be folded upwardly as shown in FIG. 95 until the connector sheet 206 at opposite ends of the panel is received between the horizontally opening J-shape channels 226 and the oblique ribs 228 of the clips. The underside of the horizontally opening J-shaped channels 226 can then be adhesively or otherwise secured to the connector sheet 206 to hold the clip in the position illustrated in FIG. 95 .
The oblique rib 228 of each clip projects beneath the connector sheet 206 so as to hold the panel in a fully expanded position. By following the same procedure at each longitudinal end of the panel, it will be appreciated that the ends of each panel will have a clip thereon and the horizontally opening J-shaped channels 226 are positioned to be secured to a flange of the T-shaped support member 60 as shown in FIGS. 84 and 85 .
An alternative way for securing a J-shaped clip to ends of the panel is shown in FIGS. 92A–95A .
As shown in FIG. 83 , the ends of the horizontally opening J-shaped channels 226 are spaced inwardly from opposite longitudinal ends of the clip 218 to accommodate a T-shaped support member 60 that extends perpendicularly to the T-shaped support member 60 to which the clip is secured. In this manner, the panels can be carried by a conventional gridwork of T-shaped support members in a suspended or supported manner with or without another set of acoustical tiles being supported by the gridwork. In other words, the panels 200 with the clips 218 secured thereto can be used in connection with an existing gridwork or in connection with a new gridwork in exactly the same manner.
A slightly modified clip 240 for the ends of the panels 200 is shown in FIGS. 101–107 .
The clip 240 is substantially similar to the previously-described clip 218 shown in FIG. 82 , the difference residing simply in the fact that the clip 240 does not have a rib 228 . In describing the clip 240 corresponding parts to the clip 218 will be assigned corresponding reference numerals with a prime suffix.
The clip is shown mounted on the compressed end of the panel in FIG. 101 where the remainder of the panel has been allowed to expand and closed into overlying relationship with the open ends of the dividers in FIG. 103 . Another difference in the clip shown in FIGS. 101–107 and the clip 218 shown in FIG. 82 resides in the fact that a channel 242 is defined between the downwardly opening channel 224 ′ and the horizontally opening channel 226 ′ with the channel 242 opening in the opposite direction to the channel 226 ′.
As shown in FIGS. 105–107 , when mounting a panel 200 having the clips 240 on the opposite ends thereof on a T-grid system wherein inverted T-shape supports 241 in the system have oppositely directed flanges 244 on which other panels 246 of a ceiling system may be supported, the clip 240 on one end of the panel is advanced onto an associated flange 244 by inserting the flange into the horizontal channel 226 ′.
Not all support systems for ceiling panels have support members of inverted T-shaped cross section. Rather, as seen in FIGS. 108 and 109 respectively, the support members 245 a and 245 b could be of generally U-shaped channeled cross section having inturned lips 247 along the two upper edges of the channeled support members.
An edge clip 251 for use with ceiling panels 50 to be supported by a channeled support system is also seen in FIGS. 108 and 109 .
Sometimes it might be desirable to fold a panel around a corner or to form a corner. With the panel used with the packaging and shipping method of the present invention, such a fold or corner can be made in an aesthetically attractive manner as illustrated in FIGS. 97 and 98 . It will be seen in FIG. 97 that a divider 208 including the connector sheet 206 across the top thereof can be severed from the remainder of the panel at the location where a fold or bend is desired in the panel leaving the outer sheet 204 where the divider was removed. The remaining portions of the panel can be folded in one direction or the other as illustrated in FIG. 98 so that one remainder portion of the panel is oriented perpendicularly to the other portion with the outer sheet 204 extending continuously around the bend so as to define a fully finished corner for the panel. Such a fold in the panel might be desirable, for example, in a skylight where a window is raised above the ceiling level into an upwardly recessed area and by following the procedure shown in FIGS. 97 and 98 , a panel or panels can be folded to extend from the normal ceiling level up into the recessed area of the skylight.
The strips of material from which the dividers 208 are made are folded in an unheated environment and a hot melt adhesive is applied to the strips or to the outer sheet 204 and connector sheet 206 before they are laminated together. Unless the panels 200 are maintained in a compressed configuration such as illustrated in FIGS. 89–91 , they will, over some period of time, expand into the configuration of FIG. 88 in which configuration the panel is no longer compressible. This time period over which it takes for the dividers to convert from the configuration of FIGS. 89–91 to the configuration of FIG. 88 is dependent upon a number of factors including the resin used in the material from which the dividers are made and also whether or not heat is applied to the material while the dividers are in the compressed configuration of FIGS. 89–91 . By adding heat to the dividers while they are compressed, the time period it takes for them to expand into the configuration of FIG. 88 is lengthened. Also, by increasing the percent of thermoplastic resin used in the material from which the dividers are made, the time in which it takes for the dividers to transform from the configuration of FIG. 89 to the configuration of FIG. 88 can be increased. By way of example only, the time period for the transformation may be varied anywhere from 15 minutes to 32 hours.
Accordingly, when the panels 200 are formed and shipped, they are desirably shipped in a compressed state so that a relatively large number of panels can be packed and shipped in a relatively small container particularly in comparison to conventional acoustical tiles of a fixed depth, i.e., a depth similar to the fully expanded depth of a panel 200 in accordance with the present disclosure for use with the packaging and shipping method of the present invention. Once the panels are removed from the shipping container, however, they expand immediately from the configuration shown in FIG. 91 through the configuration shown in FIG. 90 to the configuration shown in FIG. 89 . They will remain in the configuration of FIG. 89 for the above-noted time period after which they will transform into the configuration shown in FIG. 88 where the panel becomes incompressible from a practical standpoint.
During that time period, the panels can be cut to their desired shape and installed in a supporting grid system before the panels become substantially incompressible. They can therefore be flexed for easy insertion into the openings defined between support members in the supporting grid system if inserted before becoming incompressible.
Although the present invention has been described with a certain degree of particularity, it is understood that the present disclosure has been made by way of example, and changes in detail or structure may be made without departing from the spirit of the invention as defined in the appended claims. | A method of packaging and shipping compressible structural panels is disclosed. Compressible structural panels are provided, typically with first and second sheets separated by compressible or collapsible dividers. The structural panels are stacked and thereafter compressed thereby causing the dividers to compress and the thickness of the panels to become substantially less. In this compressed and stacked configuration, the structural panels are packaged and shipped. At the point of installation of the structural panels, the structural panels are unpackaged, unstacked and allowed to regain the expanded configuration, either by way of natural resiliency or heat setting. The structural panels, once expanded, are ready for installation. | 4 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of U.S. patent application Ser. No. 09/257,745, filed Feb. 25, 1999, now U.S. Pat. No. 6,129,850 which claims the benefit of U.S. Provisional Application No. 60/090,771, filed Jun. 26, 1998.
BACKGROUND OF THE INVENTION
The present invention relates to systems of purifying waters used in spas and jetted tubs. More particularly, the invention relates to apparatus and methods specifically configured and adapted for the treatment, for example, for the purification, of waters used in spas and jetted tubs.
Spas, jetted (hot) tubs and the like are often treated with active compounds to maintain the water therein in a purified or sanitized condition. Compounds, such as chlorine and ozone, have been used to sanitize the relatively large volumes, for example, hundreds or thousands of gallons, of water in such spas, tubs, etc. As used herein, the terms “spa” and “jetted tub” refer to systems which hold or contain a body of liquid aqueous medium, hereinafter referred to as water, which is often heated, in a reservoir which is smaller than a swimming pool, but is sufficiently large so that an adult human being can be completely submerged or immersed in the water contained in the reservoir.
Spas are often used by submerging all or a major portion of one's body in the water in the reservoir for recreation and/or relaxation. Additional, separate purifying or sanitizing components are also included in spa waters to control bacteria, algae, etc., which are known to contaminate such waters. Very low concentrations of these active materials are used in order to avoid harming sensitive parts of the body—since such spas, tubs, etc. are sized so that the entire body can be immersed in the water and to minimize costs, because of the relatively large volume of water to be treated. For example, the normal (that is the typical, non-acute contamination) concentration of ozone used to purify or sanitize the water in a spa or tub is often in the range of about 0.005 to about 0.05 parts per million (ppm) based on weight of ozone per volume of water (w/v).
Typically, ozone is generated on site for use in purifying spa/tub waters. Conventional ozone generators used for such service include a sealed ultraviolet (UV) light lamp which is known to produce ozone in the desired amounts. Such conventional ozone generators are generally effective. However, these generators do have certain drawbacks. For example, the UV light lamp is relatively bulky, can burn out (often requiring system disassembly and lamp replacement) and are relatively inefficient in producing the desired amounts of ozone.
Therefore, it would be advantageous to provide new systems for purifying waters used in spas and jetted tubs.
SUMMARY OF THE INVENTION
New systems, for example, apparatus and methods, for purifying the waters in spas and jetted tubs have been discovered. The new systems employ ozone as the purifying/sanitizing component. The ozone is generated using an assembly which is compact, durable, convenient, reliable, requires little or no maintenance and generates ozone efficiently, for example, more efficiently than a conventional UV light lamp ozone generator. Such an ozone generator is particularly effective in producing purifying amounts of ozone for spas and jetted tubs used for recreation and/or relaxation. The owners of such spas and jetted tubs want to use these items when desired, want the water to be effectively purified/sanitized, but do not want to spend large amounts of time/money on maintenance. The systems of this invention meet these requirements.
In one broad aspect, the present apparatus for purifying the water in a spa or jetted tub comprise an ozone generator and a transfer assembly. The ozone generator is sized and adapted to purify the water in a spa or jetted tube, and includes a chip electrode assembly adapted to produce ozone from air using an electric discharge. The transfer assembly cooperates with the ozone generator to pass ozone produced by the ozone generator to the water in the spa or jetted tub.
Preferably, the ozone generator is effective to produce sufficient ozone to purify (sanitize) the water in a spa or jetted tub containing about 50 or about 200 to about 1000 or about 5000 gallons of water. The concentration of ozone in the water in the spa/jetted tub is generally as noted elsewhere herein. Two or more ozone generators in accordance with the present invention can be utilized together if larger volumes of water are to be treated.
In one particularly useful embodiment, the chip electrode assembly is adapted to produce ozone from air using a corona discharge. The ozone generator preferably further includes a transformer (an electrical transformer) sized, adapted and located to control the electric power (voltage) provided to the chip electrode assembly. Often, the ozone generator operates on conventional line voltage. For example, the transformer may be adapted to function by being provided with (to be inputted with) supply (e.g., line) A.C. electric power of about 100 to about 130 volts.
Alternatively, a 12 volt D.C. system may be employed to supply electric power.
One specific ozone generator useful in the present invention is the generator sold by Del Industries under the trademark ZO-CDS or CDS16. The specifications for the CDS16 ozone generator include power: 110-120 VAC, 50/60 Hz, 90 mA and 11 W; flow: 3 SCFH or 1415 cc/min; and weight: 12 oz or 340 g.
Any suitable transfer assembly may be utilized provided that it functions to cooperate with the ozone generator to pass ozone produced by the ozone generator to the water in the spa or jetted tub.
The transfer assembly preferably includes a water pump, an adductor assembly and a transfer conduit. The adductor (or venturi) assembly has an inlet and an outlet. The transfer conduit is adapted to provide a passage for ozone-containing gases between the ozone generator and the adductor assembly. The water pump is positioned to pump water from the spa or jetted tub through the adductor assembly. The transfer conduit is positioned so that the passage of water through the adductor assembly causes ozone-containing gases from the ozone generator to pass through the transfer conduit into and through the adductor assembly.
The water pump can be, and preferably is, the spa/jetted tub water pump, that is the pump used to circulate water in the spa/jetted tub. In one useful embodiment, the adductor assembly is located in a bypass conduit and a minor amount, that is less than about 50%, of the water being pumped by the water pump is passed through the bypass line.
The transfer assembly preferably includes a water transfer line which circulates water from and to the spa or jetted tub, a filter located upstream of the adductor assembly in fluid communication with the water transfer line and adapted to remove solid or particulate matter from the water passing through the water transfer line. The transfer assembly preferably further includes a heater adapted to heat the water flowing through the water transfer line upstream of the adductor assembly.
In one embodiment, the ozone transfer conduit is configured to reduce the probability of water passing from the adductor assembly to the ozone generator. This feature is designed to avoid detrimentally affecting the ozone generator. For example, the ozone transfer conduit may include a water trap. The ozone transfer conduit may include a loop (for example, a water trap loop), preferably located above the adductor assembly, to reduce the risk of water contacting the ozone generator. The ozone generator preferably is located above the water level in the spa/jetted tub. The present apparatus may include a check valve, for example, of conventional design, located in the ozone transfer conduit and adapted to prevent fluid flow in the ozone transfer conduit toward the ozone generator.
In another embodiment of the present invention, a water purifying apparatus for a spa or jetted tub is provided which comprises a removable, replaceable chip electrode. Preferably, an ozone generator in accordance with this embodiment, generally comprises a power supply assembly housed in a main housing or enclosure, and a chip electrode assembly, separately enclosed from, and removably coupled to, the power supply assembly.
More particularly, the chip electrode assembly includes a corona discharge chip electrode housed in a separate housing or enclosure having a body portion and a cover portion. The chip electrode assembly is removably coupled to the main enclosure which houses the power supply.
Importantly, electrical connectors providing electrical connection between the power supply and the chip electrode, are adapted to be easily disengaged, thus facilitating removal of the chip electrode assembly for replacement.
For example, each electrical connector comprises a electrical contact integrated with, or mounted on, the main enclosure and a cooperating electrical contact integrated with, or mounted on, the chip electrode enclosure. In the preferred embodiment, the electrical contact on the main enclosure may comprise one or more receptacles or pins, electrically wired to the transformer or power supply, and the electrical contact on the chip electrode enclosure may comprise one or more cooperating or complementary pins or receptacles electrically wired to the chip electrode. Contact surfaces of the integrated receptacles and pins may be made of copper or other suitable conductive material.
In addition, a manually manipulable fastener, such as a thumb screw or the like, may be provided for securing attachment of the chip electrode assembly to the main enclosure and securing electrical contact between the integrated pins and receptacles. Structure may be included for enabling the chip electrode assembly to be snapped in place.
The chip electrode will eventually become worn and less effective in producing ozone over time and through repeated use. With this specific embodiment hereinabove briefly described, the worn chip electrode assembly may safely and easily be removed and replaced with a new chip electrode assembly without need for a user/consumer to open the power supply enclosure or remove the ozone generator from its location. Replacement chip electrode assemblies in accordance with this embodiment may be made available at relatively low cost.
Methods for purifying/sanitizing waters located in spas and jetted tubs are included within the scope of the present invention. Preferably, these methods comprise employing the present apparatus to provide a purifying/sanitizing amount of ozone to the water located in the spa/jetted tub.
Any combination of two or more features described herein are included within the scope of the present invention provided that the features in each such combination are not mutually inconsistent.
These and other aspects and advantages of the present invention are apparent in the following detailed description and claims, particularly when considered in conjunction with the accompanying drawings in which like parts bear like reference numerals.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a generally schematic illustration showing an embodiment of the present invention in use in purifying the water in a spa.
FIG. 2 is a plan view of the ozone generator used in the embodiment shown in FIG. 1 with the housing cover removed.
FIG. 3 is a plan view of the inner surface of the housing cover of the ozone generator used in the embodiment shown in FIG. 1 .
FIG. 4 is a top plan view of the ozone generator used in the embodiment in FIG. 1 .
FIG. 5 is a side plan view of the ozone generator used in the embodiment in FIG. 1 .
FIG. 6 is a partially cut away plan view of another embodiment of the present invention that includes a removable/replaceable flow cell.
FIG. 7 is a rear plan view of the embodiment shown in FIG. 6 .
FIG. 8 is an exploded view of the embodiment shown in FIG. 6 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to the drawings, the present purification apparatus, shown generally at 10 , includes an ozone generator, shown generally at 12 , and a transfer assembly, shown generally at 14 . Ozone generator 12 includes a housing body 16 and a housing cover 18 which is adapted to be joined or connected to the housing body by coupling threaded inserts 20 through complimentary cover holes 22 with threaded screws (not shown).
With housing cover 18 secured to housing body 18 , ozone generator 12 is in the form of a compact, closed unit. Located within the space 24 between the housing body 16 and housing cover 18 is an ozone-producing corona discharge chip electrode 26 . Ozone-containing gases produced from air, which enters housing body 16 through air inlet 27 in the housing, by chip electrode 26 exit the housing through housing outlet 28 , which can be an integral part of the housing body 16 . The air inlet may, and preferably does, include a particulate filter, for example, of conventional construction. Both the housing body 16 and housing cover 18 can be made from any suitable material or materials of construction. Preferably, these components are made of polymeric material. The ozone generator 12 typically has a length in a range of about 4 inches to about 10 inches, a width in a range of about 1 inch to about 6 inches and a thickness of about 0.5 inch to about 4 inches.
An electrical transformer 30 , of conventional design, is included within space 24 . Electrical transformer 30 processes line power, e.g., 120V, from source 32 through power cord 33 into power suitable for use by chip electrode 26 . Transformer 30 is a “step up” transformer in that the chip electrode 26 uses power having a voltage in the range of about 3000 to about 5000 volts and a frequency in the range of about 18 KHz to about 20 KHz. A series of electrical connectors 33 a, 34 and 36 are included within space 24 and are adapted to connect electric wires so as to provide electric power from source 32 ultimately to chip electrode 26 . These connectors are adapted to be easily removed to allow maintenance of generator 12 . A variable potentiometer 37 is provided and is used to control or adjust the ozone output of generator 12 .
The top 38 of housing cover 18 includes a transparent window 40 through which the spa owner can visually observe chip electrode 26 , which glows when ozone is being produced. This glow diminishes over time as the chip electrode 26 becomes less effective in producing ozone. Thus, the spa owner, by observing chip electrode 26 , is provided with an indication as to when ozone generator 12 should be replaced. Atmospheric air from air inlet 27 is directed to come in contact with the chip electrode 26 to produce an ozone-containing gas which passes through housing outlet 28 .
In addition, the housing cover 18 includes two end tabs 44 and 46 , each of which includes a through hole 48 through which screws can be passed to secure the ozone generator 12 in place in a suitable stationary position.
Ozone generator 12 operates as shown in FIG. 1 . Spa 50 includes a quantity of heated and circulating water 52 , for example, about 500 to 1000 gallons in volume. The spa 50 is equipped with a water circulating system in which water from the spa passes through spa outlet 54 into conduit 56 through spa pump 58 , spa filter 60 and spa heater 62 . Eventually the pumped, filtered and heated water is passed back to the spa 50 through return lines 64 and 66 .
In the present invention, piping segment 70 (a part of conduit 56 ), downstream of heater 62 is divided to provide a bypass line, shown generally at 72 . Bypass line 72 includes a venturi assembly 74 , of generally conventional construction, which acts as an ozone adductor to suction ozone-containing gases from ozone generator 12 into bypass line 72 . The combined ozone-containing gases and water is returned to the main water conduit 56 , as shown in FIG. 1. A valve 78 , of conventional design, is located in water conduit 79 and can be adjusted to control the amount of water passed through bypass line 72 . The ozone-containing gases from ozone generator 12 are passed through housing outlet 28 and through ozone conduit 80 into the water flowing through bypass line 72 . The suction created by venturi assembly 74 causes ozone to flow through ozone conduit 80 .
Ozone conduit 80 includes a water trap loop 82 located above venturi assembly 74 . This water trap loop 82 acts to protect the ozone generator from being exposed to water in line 56 and bypass line 72 . In addition, ozone conduit 80 includes a check valve 84 , of conventional construction, which effectively prevents fluid flow in the ozone conduit back to the ozone generator 12 . This feature inhibits, or even substantially prevents, any water from line 56 and bypass line 72 from entering ozone generator 12 .
Apparatus 10 functions as follows. When it is desired to purify/sanitize the water 52 in spa 50 , operation of the pump 58 and ozone generator 12 is initiated. This causes water 52 to flow from spa 50 through line 56 into pump 58 , filter 60 , heater 62 into piping segment 70 . At this point, a minor amount, that is less than about 50%, of the total water passing through segment 70 is caused to flow through bypass line 72 and venturi assembly 74 . This causes ozone-containing gases being generated by ozone generator 12 to pass through ozone conduit 80 into the water in bypass line 72 , which is ultimately returned to the spa via return line 64 and 66 .
Sufficient ozone is produced in accordance with the present invention to purify/sanitize the water 52 in spa 50 and/or to maintain such water in the desired purified/sanitized state.
Another advantageous embodiment of the present invention is shown in FIGS. 6, 7 and 8 . In this embodiment, the ozone generator 12 of the spa purifying apparatus 10 shown generally in FIG. 1, may be replaced with the ozone generator shown generally at 112 .
The ozone generator 112 comprises a chip electrode assembly 114 that is adapted to be removably coupled to a power supply assembly 116 .
More specifically, the power supply assembly 116 includes a power supply 120 housed and contained within a main housing or enclosure 122 comprising a main enclosure base 126 and a main enclosure cover 128 . The power supply 120 includes electrical transformer such as described hereinabove, which processes electrical power from a power source (line power of 110-120 V, or high voltage power e.g. 220-240 V) through molded plug 132 and power cord 133 .
Advantageously, the chip electrode assembly 114 is adapted to be removably coupled to the power supply assembly 116 . More specifically, the chip electrode assembly includes a chip electrode 142 , for example a corona discharge chip, shown in FIG. 8, separately enclosed from, and removably coupled to, the power supply assembly 116 . Preferably, the chip electrode 142 is housed in a separate housing or enclosure 146 , hereinafter referred to as a chip electrode enclosure, that includes a body portion 152 and a cover portion 154 . Both the main enclosure 122 and the chip electrode enclosure 146 may be made from any suitable material or materials of construction. The chip electrode enclosure portions 152 and 154 may be soldered together such that when the replacement chip electrode assembly 114 is provided to a customer/consumer, the chip electrode 142 itself is inaccessible.
Importantly, electrical connectors 160 , adapted to provide electrical connection between the power supply 120 and the chip electrode 142 are provided which are structured to be easily disengaged, thus facilitating removal of the chip electrode assembly 114 .
For example, each electrical connector 160 comprises an electrical contact, for example a receptacle 164 and cooperating pin 166 , integrated with, or mounted on, the main enclosure 122 and the chip electrode enclosure 146 respectively. Electrical wires 170 and 172 provide electrical connection from power supply 120 and chip electrode 142 to receptacles 164 and pins 166 , respectively, as shown. Contact surfaces of the integrated receptacles 164 and pins 166 may be made of copper or other suitable conductive material.
Turning now specifically to FIGS. 6 and 7, an example of electrical connections between the cell electrode assembly 114 and the power supply assembly 116 is shown. More specifically, FIG. 7 shows a diagrammatical example of the electrical wires 170 from the power supply 120 to four sets of connectors 160 (i.e. coupled pins and receptacles). The electrical wires 170 may more specifically comprise two 120V wires 173 , and two (optional) high voltage wires 174 .
Means for securing mechanical and electrical attachment between the power supply assembly 116 and the chip electrode assembly 114 is preferably provided. This may be achieved by a thumb screw 178 for example, adapted enable easy manual coupling and uncoupling of the assemblies 114 , 116 . As shown in FIGS. 6 and 8, apertures 180 are provided in both the body portion 152 and cover portion 154 of chip electrode enclosure 146 . Similarly, threaded receptacle 182 is provided in the cover portion 128 of the main enclosure 122 , wherein the apertures 180 and threaded receptacle 182 are adapted to receive the thumb screw 178 when the assemblies 114 , 116 are properly aligned. It can be appreciated that the thumb screw 178 provides means for securing mechanical attachment of the chip electrode assembly to the main enclosure as well as securing electrical contact between the integrated pins 166 and receptacles 164 . It should also be appreciated that other suitable means of securing the assemblies 114 , 116 may alternatively be provided. For example, suitable structure (not shown) may be included for enabling the chip electrode assembly 114 to be “snap fitted” onto the power supply assembly 116 .
Preferably, the chip electrode enclosure 146 includes indented, grip relief surfaces 184 for facilitating the manual removal of the chip electrode assembly 114 . Similar to as described hereinabove, with respect to the ozone generator embodiment shown in FIGS. 2-5, the chip electrode assembly 114 includes ozone supply outlet 190 to be connected to ozone conduit/supply tubing 80 (see FIG. 1 ). The ozone supply outlet 190 preferably comprises a barb member designed and structured to accommodate two different, standard tubing sizes (e.g. ¼ inch diameter and ⅜ inch diameter).
The embodiment shown in FIGS. 6, 7 and 8 is designed to enable a user (e.g. spa owner) to easily remove and replace a worn chip electrode with a new chip electrode without the need to open the power supply assembly thereby exposing the power supply/transformer. Instead, when the chip electrode becomes worn or spent, which may be evidenced, for example, by a visually observable loss of glow through a clear view window 194 , the spa owner will need perform the following simple procedure. After disconnecting cord 133 from power source, the user will (1) disconnect ozone supply tubing 80 (FIG. 1 ), (2) unscrew the thumbscrew 178 , (3) remove the old chip electrode assembly 114 , (4) install a new chip electrode assembly by aligning and connecting pins 166 with receptacles 164 , (5) secure the assemblies 114 , 116 by means of the thumbscrew 178 , and (6) reconnect ozone supply tubing 80 . Preferably, the assemblies 114 , 116 are structured accordingly to prevent misalignment between the pins 166 and receptacles 164 . In the embodiment shown, the pins 166 and receptacles 164 can not be misaligned.
Thus, it should be appreciated that a worn chip electrode assembly may safely and easily be removed and replaced with a new chip electrode assembly without need for a user/consumer to either open the power supply enclosure or remove the ozone generator from its location. Replacement chip electrode assemblies in accordance with this embodiment may be made available at relatively low cost.
The present ozone generator provides a very compact structure which: is easily and conveniently mounted for use in a spa/jetted tub application; requires relatively reduced amounts of maintenance; is cost effective to produce and use; and effectively and efficiently produces ozone in sufficient quantities to perform the desired spa/jetted tub purification/sanitation service.
While this invention has been described with respect to various specific examples and embodiments, it is to be understood that the invention is not limited thereto and that it can be variously practiced within the scope of the following claims. | Apparatus and methods for purifying the water in spas or hot tubs are provided. Such apparatus include an ozone generator sized and adapted to purify the water in a spa or jetted tub, the ozone generator including a chip electrode assembly adapted to produce ozone from air using an electric discharge, a power supply assembly, and a transfer assembly cooperating with said ozone generator to pass ozone produced by the ozone generator to the water in the spa or jetted tub. The chip electrode assembly is removably secured to and separately enclosed from the power supply assembly and is adapted to be easily, manually replaceable. | 2 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. provisional patent application, Ser. No. 60/523,440 filed Nov. 19, 2003, the entire contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
Existing cable shield contacts are known. FIG. 1 illustrates a perspective view of an existing assembled plug, shown generally as 100 . The plug 100 is similar to plugs in U.S. Pat. No. 6,358,091, the entire contents of which are incorporated herein by reference. The plug 100 includes a top cover 102 , a bottom cover 104 and a core 106 . The top cover 102 , bottom cover 104 and core 106 are all conductive to provide shielding as described herein. These conductive components may be made from metal, metallized plastic or any other known conductive material. Core 106 supports insulative (e.g. plastic) contact carriers 108 . Each contact carrier 108 includes two contacts 160 defining a pair. A boot 112 provides strain relief and is made from a pliable plastic or rubber. Also shown in FIG. 1 is cable 10 entering boot 112 . A latch 114 is provided on the top cover 102 for coupling the plug 100 to outlet (not shown).
FIG. 2 is an exploded, perspective view of the top cover 102 . The top cover includes a shield contact 164 that electrically connects the ground layer of cable 10 to the plug core 106 . Shield contact 164 is conductive and is preferably made from metal. Shield contact 164 has an arcuate portion 166 formed to generally follow the shape of cable 10 . Arcuate portion 166 includes barbs 168 that pierce the ground layer of cable 10 and the cable jacket. This electrically and mechanically connects the shield contact 164 to cable 10 . Shield contact 164 includes a pad 170 having two openings 172 formed therein for receiving two posts 176 formed in top cover 102 . The friction fit between posts 176 and openings 172 secures the shield contact 164 to top cover 102 . A tab 174 extends away from pad 170 and contacts the plug core 106 . A channel 178 is formed in the top cover 102 for receiving central ridge 144 on plug core 106 .
FIG. 3 is an exploded, perspective view of the bottom cover 104 . Bottom cover 104 is similar to top cover 102 in that both use shield contact 164 in the same manner.
In addition, FIG. 4 illustrates a graph of the calculated transfer impedance of the shield contact 164 . The dashed line illustrates the limit of the transfer impedance.
Other existing shield connection consist of single or double bar type contacts that contacted a minimal amount of cable shield area due to the non-uniform geometry of the cable and shield in the terminated state. Other solutions include U.S. Pat. No. 5,372,513 that includes an arcuate cable engagement section 122 . The same manufacturer has produced a cable engagement ground clip having a planar tab, divided into separate, planar fingers. Specifications are demanding better transfer impedance and coupling attenuation performance than existing designs provide.
SUMMARY OF THE INVENTION
The above-discussed and other drawbacks and deficiencies of the prior art are overcome or alleviated by a cable shield contact. A conductive shield contact including a plurality of fingers formed in a partial circle for contacting a cable shield, the fingers being separate elements, each finger having a first end and a second end. A partial circular member is positioned at a second end of the fingers and is connected to the fingers. A tab is formed for contacting a conductive portion of a connector to establish an electrical path between the cable shield and the conductive portion of the connector.
The above-discussed and other features and advantages of the present invention will be appreciated and understood by those skilled in the art from the following detailed description and drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
Referring now to the drawings wherein like elements are numbered alike in the several FIGURES:
FIG. 1 is a perspective view of an existing assembled plug;
FIG. 2 is an exploded, perspective view of the plug top cover of FIG. 1 ;
FIG. 3 is an exploded, perspective view of the plug bottom cover of FIG. 1 ;
FIG. 4 is a graph of the calculated transfer impedance of the shield contact of FIG. 1 ;
FIG. 5 is a front perspective view of a cable shield contact for a connector;
FIG. 6 is a bottom view of the shield contact of FIG. 5 ;
FIG. 7 is a graph of the calculated transfer impedance of the shield contact of FIG. 5 ; and
FIG. 8 depicts an exemplary cable for use with the shield contact of FIG. 5 .
DETAILED DESCRIPTION
FIG. 5 illustrates a cable shield contact 200 that can be incorporated into any existing connector (e.g., plug, outlet, etc.) and in particular into a top cover and a bottom cover of the plug, such as shown in the existing plug 100 (see FIGS. 1–3 ). Shield contact 200 is conductive and is preferably made from metal. Shield contact 200 has a plurality of fingers 202 that are formed around a diameter of a cable (not shown). FIG. 5 illustrates an exemplary embodiment of the fingers arranged in a semi-circle contacting about 180 degrees of the cable shield. The fingers 202 generally follow the shape of the cable. The fingers can also be arranged so as to cover a quarter of a diameter of the cable or about 90 degrees of the cable shield. Embodiments of the invention are not limited to specific radial coverage of the fingers and exemplary embodiments may have fingers arranged radially from about 90 degrees to about 180 degrees. The cable shield contact 200 improves as the fingers 202 cover more of the cable shield.
The plurality of fingers 202 have a first end 204 and a second end 206 . A cross-section 208 of the plurality of fingers at the first end 204 is smaller than a cross-section 210 of the plurality of fingers at the second end 206 and at member 212 . The smaller cross-section 208 provides a gripping action to the cable shield 254 ( FIG. 8 ) and may be smaller that the cross-section of the cable shield. This smaller cross-section at the first end of the fingers 202 results in a spring pressure being applied by the fingers to the cable shield. The first end 204 of the plurality of fingers 202 may be lanced to provide improved gripping action. In other words, the first end of the fingers are bent outward away from the centerline to form finger tips 203 that will be tangential to the outside surface of the cable shield when the cable is positioned between fingers 202 .
The plurality of fingers 202 are held together at the second end 206 by a member 212 . In an exemplary embodiment, member 212 is a semi-circle member that also surrounds the cable. However, member 212 can be any type of member 212 that can hold the plurality of fingers together at the second end.
In addition, the plurality of fingers 202 can move individually, which allows for individual contacts to form around the cable shield and also allows for varying surface height and contact areas. Each finger 202 is free to move up or down to contact the cable shield providing a more reliable and less resistive connection.
The fingers 202 may be inserted under the insulative, outer jacket of the cable to make electrical and physical contact with the cable shield. Alternatively, the outer jacket of the cable may be removed exposing the cable shield. The cable shield may then be peeled back over the cable jacket. The fingers 202 are then placed in physical and electrical contact with the cable shield. Tab 174 contacts connector core 106 in a similar manner as described in U.S. Pat. No. 6,358,091.
FIG. 8 depicts an exemplary cable 250 for use with shield contact 200 . The cable 250 includes an insulative jacket and a conductive shield 254 positioned beneath the insulative jacket 252 . The conductive shield 254 may be a braid, a foil, or another conductive material. As described above, apportion of the jacket 252 may be removed, as shown in FIG. 8 , and the finger tips 203 contact the conductive shield 254 . Alternatively, the jacket 252 may extend to the end of conduct shield 254 . In this embodiment, the fingers 202 are positioned beneath the jacket 252 and in contact with the conductive shield 254 .
The advantage of the shield contact 200 is that it provides a low resistance path from the cable shield (not shown) to the next physical ground path on a connector. This could be a connector shield, connecting block shield, patch panel, cable outlet box ground tab or coupler, etc. The term connector is used in a generic fashion to encompass a variety of components. In addition, the shield contact requires no additional tools and allows for different diameter cables and shield materials (foil vs. braid). Maintaining proper ground requires maintaining a low resistance connection from one point of the ground circuit to the next. If the ground path is a cable shield, when that cable is cut into to terminate to a connector, the connection of the shield to this next physical path must be low in resistance. The shield in the cable and other devices is required to maintain safe passage for high current faults as well as to provide electric immunity and electro magnetic compatibility. In other words the shield protects the internal items of the cable (electrical transmission wires) from outside electrical interference and it protects anything near the cable from electromagnetic energy emitted by the internal transmission wires. A breakdown of the path can result in excessive electrical noise being radiated outward, therefore affecting nearby electronics or it could allow outside electrical interference to penetrate into the cable and corrupt the signal on the internal transmission wires. The shield contact 200 provides a repeatable and user-friendly field termination method for cables that result in a low resistance connection to the cable shield.
The improved transfer impedance of the shield contact 200 is illustrated in FIG. 7 . There is improved electrical immunity as shown by the transfer impedance testing, which measures how well the shield terminations perform in a cable and connector. The ability to contact more of the cable shield area results in a lower contact resistance and lower conducting path for currents. Present designs for field terminable products cannot conform to the uneven surface areas involved. The fingers 202 contact the cable shield 254 and float independently from each other, which allows the shield contact 200 to conform more easily to the different surface characteristics of the cable shield. This allows more areas of contact and hence lower resistance. This design can also work for a range of cable sizes and can be incorporated in to a housing design to eliminate parts. Moreover, the shield contact 200 requires no special tool when inserting the cable to the plug.
While preferred embodiments have been shown and described, various modifications and substitutions may be made thereto without departing from the spirit and scope of the invention. Accordingly, it is to be understood that the present invention has been described by way of illustration and not limitation. | A conductive shield contact including a plurality of fingers formed in a partial circle for contacting a cable shield, the fingers being separate elements, each finger having a first end and a second end. A partial circular member is positioned at a second end of the fingers and is connected to the fingers. A tab is formed for contacting a conductive portion of a connector to establish an electrical path between the cable shield and the conductive portion of the connector. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to the art of well drilling and earth boring. More particularly, the invention relates to packer devices for closing annular space between well tubing and well casing or the borehole wall.
2. Description of Related Art
An inflatable packer is a downhole tool which can be inflated with well fluid to seal off the annular space between a well casing and a casing liner, for example. Alternatively, inflatable packers are used to seal the annulus between a tubing string and the inside wall surface of the casing, or the liner or the raw borehole wall.
The utilities for inflatable well packers are myriad. They may be used to support a column of cement above a lost circulation zone. They may also be used to isolate producing zones from cement contact. At times they are used to centralize a casing during cementing operations. Also, they may be used to isolate production zones from lost circulation zones for gravel pack operation.
Inflatable packers of the prior art typically provide structures for reinforcing and protecting the inflatable bladder. Most frequently, these structures take the form of woven or braided steel cable or a cladding of lapped steel ribs. In the case of braided cable reinforcement, a closed tube of braided material is secured at opposite ends to the packer end collars by a compression assembly between a pair of conical clamping surfaces in a manner similar to that disclosed by U.S. Pat. Nos. 4,191,383; 4,372,562; and 4,424,861. In some cases, the end attachment of braided reinforcement is supplemented by epoxy polymer that is injected into the braided cable interstices between the conical clamping surfaces.
Lapped steel ribs for packer reinforcement are secured to the respective end collars by means of a corner weld between the end-face formed by the lapped strip ends and the inside bore surface of the packer end collars. U.S. Pat. Nos. 5,143,154; 5,280,824; 5,361,479; 5,363,542; and 5,439,053 illustrate this latter type of packer reinforcement and assembly.
When the bladder element of a reinforced packer is expanded, the reinforcing element is at risk of structural failure. In the case of a lapped rib reinforcement, the usual point of failure is along the corner-weld bead.
It is an object of this invention, therefore, to strengthen the structural attachment of packer reinforcement ribs to the packer end collars.
Another object of the invention is to provide additional lines and means of lap rib attachment to packer end collars.
Also an object of the invention is the provision of structural redundancy for securing lapped rib reinforcement to a packer end collar.
A still further object of the invention is to double, in some cases, the force required to separate a lapped rib assembly from a packer end collar.
An additional object of the invention is to increase the ultimate tensile strength of the reinforcing rib assembly for an inflatable packer by distributing the load on the ribs over a larger area and thus reducing the stresses on a single weld or single line of attachment to the inflatable element sleeve.
SUMMARY OF THE INVENTION
These and other objects of the invention are accomplished by an inflatable well packer of the ribbed type in which the ribs are secured to the inside bore of the packer sleeves by a plurality of welds and by a low temperature bonding material such as an injection molded epoxy resin.
The packer ribs are assembled and held by a welding jig in the required end-weld position relative to a packer end sleeve. Preceding the end sleeve, in coaxial assembly over the jig held ribs, a cylindrical stress ring and a bonding ring are loosely positioned. The packer end sleeve is positioned over the jig confined ribs and the ribs are end-welded to the interior bore of the end sleeve. Next, the outer annulus of the bonding ring is positioned adjacent to the inner annulus of the of the end sleeve with a small separation gap therebetween. This separation gap is filled with one or more circumferential weld beads with care given to fuse the bonding ring and end sleeve material with the outer elements of the rib material
An axial length segment of the bonding ring is undercut and vented with one or more radial borings to facilitate the injection and circumferential distribution of a low temperature bonding agent such as epoxy or polyester resin around the circumference of the rib assembly. Preferably, the bonding agent is injected and cured after the fusion welding is completed. The bonding agent support may be used in conjunction with the circumferential weld bead or independently thereof.
If not an integral portion of the bonding ring, a stress ring is positioned coaxially over the ribs and axially against the inner end annulus of the bonding ring. Preferably, the stress ring is secured with a crimped lip.
With both ends of the ribs secured to the end sleeves and bonding rings, one or more outer cover segments of elastomer are either calendared onto or molded about the perimeter of the rib assembly between the end sleeves. The cover segments are bandaged and the entire assembly is heat cured. If so provided, the bonding agent may be simultaneously heat cured.
After completion of the rib and cover segment assembly, the inflation bladder is inserted within the rib enclosure and secured by such means as a wedge ring.
BRIEF DESCRIPTION OF THE DRAWINGS
For a thorough understanding of the present invention, reference is made to the following detailed description of the preferred embodiments, taken in conjunction with the accompanying drawings in which like elements have been given like reference characters throughout the several figures of the drawings:
FIG. 1 is an axial length quarter section of a well packer incorporating the present invention;
FIG. 2 is an enlargement of the FIG. 1 area designated by the perimeter of enclosure A of FIG. 1;
FIG. 3 is a partial section of an alternative sleeve configuration;
FIG. 4 is an axial length quarter section of a third embodiment of the invention; and
FIG. 5 is a partial section of a fourth embodiment of the invention.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to drawing FIG. 1, the assembly designated generally by reference character 10 is the inflatable element of a more expansive packer assembly having similarities to that of U.S. Pat. No. 4,372,562. In particular, the inflatable element 10 concentrically overlies a cylindrical or tubular mandrel having a central, fluid carrier bore axially through the packer assembly. In particular, the inflatable element provides a fluid tight seal between the mandrel and opposite ends of the inflatable element.
Opposite ends of the inflatable element 10 comprise the axial alignment of an inner sleeve 12 , and outer ring 14 and a stress ring 16 . Adjacent annular ends of the inner sleeve 12 and the outer ring 14 are beveled to facilitate joinder of the ends by a circumferential weld bead 24 . The opposite end of outer ring 14 is machined to provide a circumferential lip 29 that is rolled, peened or crimped into the crimp channel 25 around the outer perimeter of the stress ring 25 .
The internal bore wall of the outer ring 14 includes a circumferential undercut 26 as shown by FIG. 2 . The undercut is ported by one or more injection apertures 28 .
Secured to the internal bore of the inner sleeve 12 by means of a corner or filet weld 22 is a cylindrical assembly 20 of lapped, stainless steel ribs. The outer circumferential elements of the lapped ribs lie adjacent to the internal bore walls of the outer ring 14 as well as the stress ring 16 and thereby span across the undercut 26 in the outer ring 14 and the weld bead 24 . The weld bead 24 fuses the outer perimeter elements of the ribs 20 with the end elements of the inner sleeve 12 and the outer ring 14 thereby integrating the sleeve 12 and ring 14 into a singular end sleeve unit.
A low temperature bonding agent secures the outer perimeter elements of the ribs 20 to the outer ring 14 across the undercut 26 . Preferably, such a low temperature bonding agent is a polymer resin such as an epoxy or polyester compound that may be injected into the undercut 26 through the port(s) 28 . However, some applications may find greater utility for a braze metal or high-strength solder. Each of these low temperature bonding agents have distinctive properties and useful applications as are well known to the art. The phrase “low temperature bonding agent” is used to distinguish the physical characteristics of a weld that fuses and mixes the base metals of a joint from those of a superficial adhesion or molecular interface bonding.
After the ribs 20 are secured to the integrated sleeve and stress ring 16 , the elastomer bladder 30 is positioned within the internal rib tube and secured at respectively opposite ends by wedge rings 32 . These rings 32 have a conical end face 33 and threaded serrations 34 around the outer perimeter. The wedge rings 32 are pressed into the sleeve bore to compress the tubular ends of the elastomer bladder 30 against the smoothed corner weld bead 22 . A locking ring 36 is turned on threads 38 into the outer face of the wedge ring 32 to secure and maintain the compressive force on the bladder 30 .
The outer perimeter of the lapped rib assembly 20 is girdled by one or more outer covers 40 of elastomer material such as natural or nitrile rubber. When the bladder 30 is expanded, these outer covers provide the contact interface to seal the packer structure to the surrounding wall.
The individual rib elements 20 are preferably fabricated of a high tensile strength steel. A stainless steel composition is a further fabrication preference. After forming, shaping and if required, heat treating, the individual rib elements are surface distressed as by sandblasting or knurling for example for the purpose of promoting a bonded interface with the low temperature bonding agent used in the undercut. The outer ring 14 may also be surface distressed at and along the sleeve undercut 26 and other locations corresponding to the low temperature bonding agent.
After the assembly preparation, the individual rib elements are brought together in an assembly jig and held at the required tubular position while the stress rings 16 and outer rings 14 are positioned loosely over the tube ends. Next, an inner sleeve 12 is positioned over the respective tube ends and the ends of the ribs are welded to the inside bore wall with a corner weld 22 .
The outer ring 14 is then positioned end-to-end with the sleeve 12 . Depending on many variables, a gap of about ⅛ in., for example, may be set between the adjacent ends. Between the adjacent sleeve and ring ends, a circumferential weld bead 24 is laid in one or more weld passes. The first of these passes is set fuse elements of the ribs 20 into the bead that includes the sleeve 12 and ring 14 edges.
When the welding procedures have been completed, the desired low temperature bonding agent is applied between the ribs 20 and the outer ring 14 . In the case of a polymer resin such as epoxy or polyester, the compound may be injected through the injection port 28 into the under cut 26 for distribution around the rib tube 20 perimeter. The resin may be a catalyst cured or, if desired, heat cured in cooperation with the preparation of the outer covers 40 .
Alternatively, the low temperature bonding agent may be braze metal or silver solder and preapplied to the undercut. After the rib assembly 20 is in place, the low temperature flow metal is heated conductively through the outer ring 14 and caused to flow between the lapped ribs. In another example, the braze or solder may be caused to flow through the aperture 28 for distribution around the rib tube.
Following placement of the low temperature bonding agent, the stress ring 16 is positioned adjacent to the inner edge of the ring 14 and under the crimp lip 29 . Here, the lip 29 is either crimped, peened or rolled into the crimp channel 25 to unitize the stress ring with the sleeve.
The outer covers 40 are next fabricated by a wrapped layup of rubber or other suitable polymer or by an injection mold of such material. The rough mold or layup is then tightly wrapped (bandaged) with a binder fabric such as nylon and heat cured. The curing procedure may also include the polymer resin that was used between the ribs 20 and the outer ring 14 . When the curing step is complete, the bandaging is removed and the outer covers are dimensionally sized.
At this point, the premolded bladder tube 30 is inserted through the ribbed tube 20 and the wedge ring 34 pressed into compressed position against the corner weld bead 22 . Finally, the lock ring 36 is turned over internal threads 38 to secure the assembly.
Tests conducted on several permutations of the invention include those for ultimate tensile load to provide a strength comparison baseline. These tests included a tube of 80 ribs that were secured at opposite ends to respective end sleeves by corner welds between the rib ends and an internal bore of each sleeve. The sleeve material was 1030 carbon steel. The ribs were 0.015 in. thick×0.750 in. wide×16.00 in. long and of 301 stainless steel material. The rib tube layup mandrel had a 2.362 in. o.d. The average ultimate load sustained by the test examples was 64,000 pounds.
Additional test examples were fabricated in conformance with those above except that the sleeve bores were undercut and injected with epoxy resin. Rib tubes respective to the test examples were secure to the sleeves by both end welding and by epoxy bonding. The average tensile loads sustained by these examples was 110,000 pounds: an increase of 72% over the baseline configuration.
A second baseline configuration was constructed having 130 stainless steel ribs distributed around a 3.000 in. o.d. layup mandrel. The rib tube was end welded to carbon steel sleeves. The ribs were 0.020 in. thick, 1.000 in. wide and 16.00 in. long. The average ultimate load sustained by this baseline configuration was 237,500 pounds. A modification of this second baseline configuration additionally included one circumferential weld bead about the rib tube o.d. The modified test specimen sustained an average ultimate load of 332,500 pounds: an increase of 40% over the baseline configuration.
The FIG. 3 invention embodiment includes two supplemental sleeve rings 42 and 44 between the inner sleeve 12 and the stress ring 16 . In this case, the inner sleeve 12 is corner welded to the rib tube 20 outside perimeter with a first tube O.D. bead 50 . This first tube O.D. weld 50 is additional to the traditional rib end bead 22 .
Thereafter, the first outer ring 42 is positioned and secure to the inner sleeve 12 with a first sleeve O.D. bead 52 .
Next, the second rib tube O.D. bead 54 is applied followed by a second sleeve O.D. bead 56 that secures the second outer ring 44 to the first outer ring 42 . In this example, the stress ring 16 is secured to the second outer ring 44 in a manner corresponding to that of FIG. 2 . It will be understood, however, that the stress ring 16 may be secured by means of a weld bead if desired.
A third embodiment of the invention, illustrated by FIG. 4, incorporates an integral or single piece sleeve 62 having a stress relieving end nose 69 . This third embodiment includes no welded connection between the rib tube and the sleeve 62 . Instead, the rib tube end is welded to an independent collar 64 and the sleeve and collar are coaxially engaged mechanically against respective abutment faces. The internal bore of the sleeve includes a counterbored inside step-face 68 . The reinforcing rib tube 20 is end-welded with a bead 66 to the end of the rib collar piece 64 . The rib collar 64 includes an outside step-face 65 that mechanically engages the inside step-face 68 of the sleeve. If desired, a low temperature bonding agent may be applied to the inside bore wall of the sleeve 62 and /or the outside perimeter of the rib tube 20 prior to coaxial assembly and induced to flow together after assembly by heat or capillary force.
The fourth invention embodiment of FIG. 5 also includes a single piece sleeve 82 in which the internal bore is undercut with a cavity 86 . The cavity is ported by injection apertures 88 for insertion of a low temperature bonding agent as previously described. As with the FIG. 4 embodiment, the ribs 20 are end-welded by a bead 66 to a collar 64 that mechanically interlocks with mutual engaging step-faces 65 and 68 . Following coaxial assembly, the cavity 86 is injected with epoxy resin, for example.
Although our invention has been described in terms of specified embodiments which are set forth in detail, it should be understood that this is by illustration only and that the invention is not necessarily limited thereto, since alternative embodiments and operating techniques will become apparent of those of ordinary skill in the art in view of the disclosure,. Accordingly, modifications are contemplated which can be made without departing from the spirit of the described invention | An inflatable packer or bridge plug utilized in well bores comprises a tubular elastomeric bladder that is circumferentially surrounded by flexible metallic rib elements. At opposite ends of the packer, the ribs are secured to the inside bore of respective end sleeves by welding and by non-welded bonding. The rib ends are corner bead welded to the end sleeve bore wall to overlie a circumferential undercut of the sleeve bore wall. A second, circumferential weld bead fuses an adjacent sleeve ring to the first and integrates peripheral elements of the ribs. One or more radial vents into the undercut facilitates distribution of a low temperature bonding compound such as epoxy or polyester resins or braze metal or solder. The welding procedures are carried to completion before the bonding agents are applied. | 4 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates generally to systems and methods for context-aware computing, and more particularly for context-aware computer management using a smart badge.
[0003] 2. Discussion of Background Art
[0004] Context-aware computing is a field of computer science where computers are provided with sensors for detecting their orientation with respect to persons, places or things. Smart identification badges are an example of context-aware computing devices which contain an array of mini-sensors and wireless technologies for gathering information on their environment and communicating with other computers in order to provide such services as unlocking doors, and selective access to sensitive database information within various secure environments.
[0005] The mini-sensors can use a variety of biometric and standard technologies to monitor environmental conditions such as light, humidity, temperature, and sound levels, as well as spatial motions, voice patterns, and perhaps pheromones. Software programs then process this sensor information to conclude such things as who is wearing a smart badge and for how long. Researchers in the area of context-aware computing include Dr. Mark Smith at Hewlett-Packard Labs in Palo Alto and Gerald Maguire, professor of data communications at the Swedish Royal Institute of Technology.
[0006] Dr. Smith, for example, has developed a badge size SecurePAD which an employee picks up each morning, registers and authenticates in a secure booth, and carries on their person while at work. The badge communicates with beacons distributed throughout an office environment which respond to the badge by selectively opening doors and providing predetermined sets of information and functionality on secure computer systems. At the end of the day the badge is selectively inactivated. Presideo Inc., of Sebastian, Fla. also manufactures similar security systems as described on their web site at http://www.presideo.com.
[0007] [0007]FIG. 1 is a dataflow diagram of a prior art system 100 for interfacing with smart identification badges. In the system 100 credentials for several wearers are authenticated and downloaded into their respective smart badges 102 , 104 , 106 , and 108 . A computer 110 connected to a narrow infrared (IR) beacon 112 selectively communicates with the badges 102 - 108 . The beacon 112 by design has a short distance and narrow visibility range so that only one smart badge worn by an employee sitting right in front of the computer 110 is visible to the beacon 112 at any one time. The prior art considers this narrow range of visibility as a way to increase the system's 100 overall security.
[0008] A system service module 114 within the computer 110 communicates 111 with the smart badges through the beacon 112 . When a first one 104 of the smart badges 102 - 108 becomes visible to the beacon 112 , the service 114 queries the badge 104 for a set of credentials and, if the credentials are authentic, instructs the computer 110 , perhaps using Microsoft Corporation's Graphical Identification and Authentication (GINA) 116 and OS Logon 118 modules, to log the employee carrying the badge 104 on to the computer 110 . If the badge 104 is no longer visible to the beacon 112 , the service 114 the GINA 116 to lock the computer 110 and blank the computer display even though the employee remains logged on. Then, should the badge 104 become visible again, the service 114 instructs the GINA 116 to unlock the computer 110 and reactivate the computer display. If a second smart badge 106 becomes visible 120 to the computer 110 , during a time when the first badge 104 is invisible to the beacon 112 , the system service 114 instructs the GINA 116 to log-off the employee assigned to the first badge 104 , and log-on the employee assigned to the second badge 106 .
[0009] The system 100 is limited to allowing only one wearer to be logged on at any one time and requires that such wearer sit right in front of the computer 110 before unlocking the computer and display. Database security is thus achieved by logging only one wearer on a time. The wearer then runs a software application to access data in the database. The GINA's 116 role in controlling access to the database is by controlling which wearer logs on to the computer 110 . In many operational settings, however, such an implementation is awkward to use. Furthermore, the prior art system 100 does not even begin to exploit the smart badge's 102 - 108 full capabilities for providing contextual information to the computer 110 .
[0010] What is needed is a system and method for context-aware computer management using a smart badge that overcomes the problems of the prior art.
SUMMARY OF THE INVENTION
[0011] The present invention is a system and method for context-aware computer management. The method of the present invention includes the steps of: assigning database information one of several clearance levels; assigning each smart badge within a set of visible smart badges one of the clearance levels; identifying smart badges having a lowest clearance level; and providing access to database information having clearance levels no higher than the lowest clearance level.
[0012] In other aspects of the invention, the method may include the steps of: configuring a predetermined smart badge visibility range; updating the set of visible smart badges in response to a change in smart badge visibility status, and recalculating the lowest clearance level in response to the change in smart badge visibility status; recording the smart badge visibility status of each smart badge within an activity log; preventing database access to smart badge wearers when the wearer's smart badge visibility status is set to invisible longer than a predetermined timeout; reading and writing data items from and to the smart badges; defining a badge removal confidence level indicating whether each smart badge has been continuously worn by corresponding assigned smart badge wearers; assigning a smart badge time-to-live parameter to each of the smart badges; and inactivating a smart badge whose time-to-live parameter has been exceeded.
[0013] The system of the present invention includes a database storing information differentiated by a plurality of clearance levels; a wide-angle RF beacon; a set of smart badges, in communication with the beacon, each badge assigned one of the clearance levels; a system service module, connected to the beacon, for identifying a lowest clearance level assigned to the smart badges; and a software application, connected to the service module and the database, for providing access to information within the database having clearance levels no higher than the lowest clearance level.
[0014] In other aspects of the invention, the system may include a second diffuse IR beacon, coupled to the service module, for location awareness and perhaps limited to detecting smart badges within a workroom; the smart badges may also include biometric sensors for detecting when a smart badge has been removed from an assigned smart badge wearer.
[0015] The system and method of the present invention are particularly advantageous over the prior art because a customizable software application provides access to information based on clearance levels of those smart badge wearers visible to the beacons. Also, the wide angle first beacon enables the service module to monitor and communicate with all smart badges within a predefined area instead of just those smart badge wearers very close to or in front of the system.
[0016] These and other aspects of the invention will be recognized by those skilled in the art upon review of the detailed description, drawings, and claims set forth below.
BREF DESCRIPTION OF THE DRAWINGS
[0017] [0017]FIG. 1 is a dataflow diagram of a prior art system for interfacing with smart identification badges;
[0018] [0018]FIG. 2 is a dataflow diagram of an embodiment of a system for context-aware computer management using smart badges; and
[0019] [0019]FIG. 3 is a flowchart of an embodiment of a method for context-aware computer management using smart badges.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0020] [0020]FIG. 2 is a dataflow diagram of an embodiment of a system 200 for context-aware computer management using smart badges. The system 200 includes a computer 202 coupled to a first wireless beacon 204 , a second wireless beacon 206 , and a database 208 . The system 200 also includes one or more smart badges 210 , 212 , 214 , and 216 in communication with the computer 202 through the beacons 204 , 206 . The computer 202 may or may not be networked with other computers in a client/server topology.
[0021] The smart badges 210 - 216 are context-aware devices which improve upon a design developed by Dr. Mark Smith at Hewlett-Packard Labs in Palo Alto called SecurePad. The badges communicate with the beacons 204 , 206 using either Radio Frequency (RF) and/or Infrared (IR) technology. The badges contain various biometric and other sensors for detecting and monitoring the badges' surroundings, including those persons wearing and/or objects affixed to the badges. While the following specification discusses an embodiment of the present invention where the badges are worn by people in a workroom, those skilled in the art will recognize that the present invention in other embodiments can be used in a variety of other applications.
[0022] The smart badges are preferably activated, and initialized within a standard security booth. Within the booth a smart badge wearer follows a traditional security protocol (i.e. such as typing a password on keyboard, or displaying a finger print) to activate and initialize a badge. As part of initialization all smart badge credentials are reset, previously stored data is erased, and a new set of data may be downloaded into a data storage area within the smart badge.
[0023] The first beacon 204 includes a transmitter and a receiver for establishing a communications link between the computer 202 and the smart badges 210 - 216 . The first beacon 204 is preferably a wide angle device which can simultaneously detect and communicate with several smart badges. The first beacon 204 preferably communicates with the smart badges using an RF signal. RF signals can pass through walls, doors, file cabinets and other blocking objects and thus provides a more reliable communications link than IR. The second beacon 206 is preferably a diffuse IR device which works in conjunction with an RF first beacon 202 . Since walls, doors, window, and etc. block IR signals, the second beacon 206 helps the computer 202 distinguish between smart badges within the workroom and smart badges passing by in a hallway outside of the workroom.
[0024] The database 208 preferably stores information having a plurality of confidentiality levels. Each smart badge wearer may have one of several different clearance levels assigned to their smart badge during the activation and initialization procedure. For example, if the information includes confidential patient medical records within a hospital setting, a first smart badge wearer, who is a doctor, may have a clearance level permitting accessibility to a first set of records and/or fields in the database 208 , while a second smart badge wearer, who is a nurse, may have a clearance level permitting accessibility to a second set of records and/or fields in the database 208 , which may or may not overlap with the first set of records and fields. Those skilled in the art recognize that the information in the database 208 could alternatively be business records in a corporate setting, financial records at a bank, or any other type of information.
[0025] While the entire system 200 is preferably located within the workroom, only some sort of user interface (e.g. a display terminal and a keyboard) and the second beacon 206 need to be located within the workroom.
[0026] Within the computer 202 there is a system service module 218 , an activity log 220 , and a software application module 222 . The computer 202 is initially and preferably booted up by a trusted system administrator, after which the system service 218 is automatically activated as a background process. The system administrator then logs on to the computer 202 using standard logon procedures. Once logged on, the administrator launches the software application 222 .
[0027] The service module 218 is coupled to the first beacon 204 , the second beacon 206 , the activity log 220 and the software application 222 . Software within the service module 218 normally operates as an ongoing background process responsive to entry and exit of smart badges from the workroom. Those skilled in the are will recognize that while the system service 218 is described with reference to a Microsoft Corporation Windows NT environments consisting of background services, functionality within the system service 218 module could easily be implemented by demons within a UNIX environment, or in another application program. Throughout operation, the service module 218 continually records and updates a variety of context-aware information in the activity log 220 regarding the smart badges 210 - 216 , their status, and configuration.
[0028] The application 222 provides database 208 access to only a predetermined set of smart badge wearers. The application 222 also includes database management code for selectively retrieving and displaying sets of records and/or fields within the database 208 corresponding to the clearance level of each smart badge wearer within the workroom. The application 222 also may provide differing levels of software application functionality based on the clearance levels. Thus, the application provides data access security by cooperating with the system service 218 and consulting the activity log 220 for a list of wearers present within the workroom and their corresponding clearance levels. Preferably, the wearers are not actually logged on and off of the computer 202 , but rather are either provided or denied access to the database 208 and functionality on the computer 202 .
[0029] Returning to the hospital setting example, when the doctor is in the workroom, the application 222 permits retrieval and display of the first set of records and fields, however, should the nurse enter the workroom, the application 222 preferably permits retrieval and display of those records and fields which are common to the first and second sets of records and fields. Later, should a receptionist enter the workroom who does not have clearance to see any of the records or fields, the application 222 may deny access to all records and fields, and blank the computer display, even though the doctor and nurse are still in the workroom. Those skilled in the art will recognize that when information is or is not retrievable and displayed depends upon each implementation of the software application 222 .
[0030] [0030]FIG. 3 is a flowchart of an embodiment of a method for context-aware computer management using smart badges. The method begins in step 302 where wearers enter a secure booth and authenticate their smart badge. During authentication, the smart badge is reset to an initial state. Resetting the badge erases all prior credentials and stored data.
[0031] In step 304 , the service module 218 configures the beacons 204 , 206 to a predetermined smart badge field of visibility. While preferably, smart badge visibility is defined as those smart badges which are in communication with both beacons 204 and 206 , smart badge visibility range can also be adjusted by limiting transmitter power or receiver sensitivity of the smart badges 210 - 216 , the first beacon 204 , and/or the second beacon 206 . In this latter, less favored implementation, first, the first and second beacons' 204 , 206 transmitter output and the receiver sensitivity of the smart badges 210 - 216 are all set at their maximum to ensure that the computer 202 can send commands to the smart badges 210 - 216 . Then smart badge visibility is limited through predetermined adjustments to the beacons' 204 , 206 reception sensitivity and/or the smart badges' 210 - 216 transmitter power.
[0032] In step 306 , the service module 218 establishes communications with all visible smart badges. As discussed before, the smart badges 210 - 216 which are visible are preferably all located somewhere within the workroom.
[0033] Next in step 308 , the service module 218 configures each of the visible smart badges. As part of configuration, the service module 218 defines a VisibleTimeout variable which specifies a predetermined period of time during which one or more of the smart badges can be invisible to (i.e. out of communication with) one or more of the beacons 204 , 206 .
[0034] The service module 218 can also set a variety of other smart badge variables, such as a TimeToLive variable, a LostBadgeTimeout variable, as well as internal clock and calendar variables. The TimeToLive variable sets an expiration period for the smart badge, which upon expiration, the smart badge automatically de-authenticates itself and erases all internally stored data. Preferably, the TimeToLive variable is set to a little longer than a standard work day.
[0035] The LostBadgeTimeout variable, specifies a time before the smart badge sounds an audible alarm, such as a beep, once the biometric sensors in the smart badge determine that the badge is no longer on the wearer. Preferably the LostBadgeTimeout variable is set to one hour.
[0036] In step 310 , when a smart badge is no longer visible the service module 218 changes that smart badge's status to invisible in the activity log 220 and sends a smart badge timeout message to the application 222 . The VisibleTimeout variable permits badge wearers to walk throughout the workroom and be invisible for a predetermined period of time without being identified within the activity log 220 as invisible. Preferably the VisibleTimeout predetermined period of time is set to five seconds.
[0037] In step 312 , every 500 msec or so the service module 218 sends out a general transmit heartbeat command to all smart badges within the workroom. In response, each smart badge transmits a heartbeat status message to the service module 218 , which is received by the service module 218 in step 314 .
[0038] The heartbeat status message includes a predetermined set of badge status information, such as: smart badge identification (ID) number; badge removal confidence; badge removed; time-to-live; reset state; activation state; initialization state; badge activated; badge initialized; ID card on badge; ID card removed at least once; and battery state of charge. Note, the ID card is preferably a standard employee site badge. During authentication, wearers are required to insert their ID card in a slot on top of their smart badge. A sensor on the smart badge detects whether the ID card remains in the slot. Those skilled in the art will recognize that many other codes may also be included in the heartbeat.
[0039] The smart badge ID number is unique and permanently stored within each smart badge. The badge removal confidence is a variable which indicates a confidence level that the smart badge has been continuously worn by the smart badge wearer. Badge removal confidence is programmed by the smart badge's biometric sensors to between “0 to 7,” where “0” indicates with certainty that the badge was worn at all times by the wearer, and “7” indicates with certainty that at some time the badge was worn by a different wearer.
[0040] In step 316 , the service module 218 stores each smart badge's heartbeat status and status changes in the activity log 220 . Smart badge status changes include smart badge wearer enters the workroom, smart badge wearer leaves the workroom, and heartbeat status changes.
[0041] In step 318 , the service module 218 responds to requests from the software application 222 for information stored within the activity log 220 . In step 320 , the software application 222 selectively displays information on the computer display in response to the activity log information and the application's 222 programming. In step 322 , the software application 222 also selectively provides functionality on the computer 202 in response to the activity log information and the application's 222 programming. In step 324 , the service module 218 updates the activity log 220 as smart badge status changes.
[0042] In step 326 , the service module 218 read and/or writes binary data from/to the smart badge in response to commands from the application 222 . Data items may include security passwords/cookies and/or other wearer specific personalized data. The data is preferably password protected and communication between the service module 218 and the smart badge can be either synchronous or asynchronous. Asynchronous data transfer tolerates a momentary loss of smart badge visibility during data transfer, such as when wearer moves about the workroom.
[0043] In step 328 , the service module 218 periodically pre-reads a predetermined set of frequently used data from the smart badges. Pre-reading is defined as when the service module 218 reads data items from the smart badge during otherwise idle times when the badge is visible to the beacon 204 , but no communications between the service module 218 and the badge are otherwise required. The pre-read function enables the software application 222 to be more responsive.
[0044] In step 330 , the service module 218 selectively deletes data items from the smart badge in response to application 222 commands.
[0045] While one or more embodiments of the present invention have been described, those skilled in the art will recognize that various modifications may be made. Variations upon and modifications to these embodiments are provided by the present invention, which is limited only by the following claims. | A system and method for context-aware computer management is disclosed. The method of the present invention includes the steps of, assigning database information clearance levels; assigning smart badges one of the clearance levels; identifying smart badges having a lowest clearance level; and providing access to database information having clearance levels no higher than the lowest clearance level. The system of the present invention includes a database storing information differentiated by several clearance levels; a beacon; a set of smart badges, in visible communication with the beacon and assigned one of the clearance levels; a system service module, connected to the beacon, for identifying a lowest clearance level assigned to the smart badges; and a software application, connected to the service module and the database, for providing access to information within the database having clearance levels no higher than the lowest clearance level. | 6 |
TECHNICAL FIELD
[0001] The present invention relates to a method for detecting methylated cytosine in DNA using conversion of non-methylated cytosine into uracil by bisulfite reaction.
BACKGROUND ART
[0002] It has been known that methylation of genomic DNA in a living organism is caused to suppress expression of mRNA. Further, it has been reported that the difference of methylation pattern on a genome relates to genesis, differentiation, and disease such as cancer, and therefore the analysis of methylation of genomic DNA has an important role in finding out the cause and prevention of disease, development of medicinal products, research on the regenerative medicine, and so on.
[0003] On the other hand, as the method for determining methylated cytosine in DNA nucleotide sequence, a method for comparing the fragments by methylation-sensitive restriction enzyme, a bisulfite method, a methylation-specific PCR method, and a method which utilizes a high performance liquid chromatography (HPLC), etc have been known. Among them, the bisulfite method has become popular as a common method because the bisulfite method is low cost and applicable to high throughput, and is also effective for sequencing and screening.
[0004] However, since conversion rate from non-methylated cytosine into uracil is not high in said bisulfite method, the bisulfite method had problems of low accuracy etc. in detection of methylated cytosine. Therefore, until now, development of a bisulfite method having high accuracy has been desired.
[0005] In addition, the DNA which had been subjected to the bisulfite reaction was inferior in storage stability because non-methylated cytosine is converted to uracil. That is, even if the gene which was subjected to the bisulfite reaction was intended to use again, the period during which the gene can be stored stably was only about several days. Therefore, in order to utilize it again, usually the one amplified by the PCR had to be stored. However, since only specific DNA was amplified in the one subjected to the PCR reaction, it was not suitable for storing with libraries in the genome reserved. Therefore, the development of a method for obtaining a DNA after bisulfite reaction, which can be stored with libraries in the genome reserved is excellent in storage stability, has also been desired.
SUMMARY OF THE INVENTION
Problem to be Solved by the Invention
[0006] It is an object of the present invention to provide a method for obtaining a DNA after bisulfite reaction, which can be stored with libraries in genome reserved and has excellent storage stability, and also to provide a method for detecting methylated cytosine more accurately as compared with the conventional bisulfite reaction.
Means for Solving the Problem
[0007] In view of the above-described situation, the present inventors have investigated extensively to develop a bisulfite method having high accuracy. As a result, the present inventors have found that a single-stranded DNA obtained by subjecting the single-stranded DNA which has been subjected to the bisulfite reaction to reverse transcriptase reaction was excellent in storage stability due to not including uracil., and thus the present invention has been achieved. In addition, since the said single-stranded DNA is a solution before the PCR reaction, libraries in the gene was reserved. Therefore, as described above, the single-stranded DNA obtained by subjecting single-stranded DNA to the bisulfite reaction and to the reverse transcriptase reaction was excellent in storage stability and also was kept the library reserved, which solved the problems of the conventional method. Usually, the reverse transcriptase reaction is not carried out using DNA as a template, and therefore, as described above, the subjecting the bisulfite-reacted DNA to the reverse transcriptase reaction as a template was the first trial carried out by the present inventors. Further, it was unexpected that such effect could be acquired by the trial.
[0008] Furthermore, it was found that, by subjecting the reaction product obtained by subjecting the single-stranded DNA to the bisulfite reaction and reverse transcriptase reaction, to the PCR, the single-stranded DNA, in which non-methylated cytosine has been uracilated, could be amplified efficiently, and thus attained the present invention.
[0009] That is, the present invention relates to “a method for obtaining DNA complementary to a single-stranded DNA in which non-methylated cytosine has been uracilated, comprising subjecting the single-stranded DNA to 1) bisulfite reaction and 2) reverse transcriptase reaction in this order (hereinafter, sometimes abbreviated as a method for obtaining complementary DNA of uracilated DNA of the present invention)”, “a method for amplifying DNA complementary to a single-stranded DNA in which non-methylated cytosine has been uracilated, comprising subjecting the single-stranded DNA to 1) bisulfite reaction, 2) reverse transcriptase reaction and 3) PCR reaction in this order (hereinafter, sometimes abbreviated as a complementary DNA amplifying method of uracilated DNA of the present invention)”, and “a method for detecting methylated cytosine in a single-stranded DNA, comprising subjecting the single-stranded DNA to 1) bisulfite reaction, 2) reverse transcriptase reaction 3) PCR reaction in this order, and subjecting the obtained PCR amplification product to nucleotide sequence analysis (hereinafter, sometimes abbreviated as a method for detecting methylated cytosine of the present invention)”.
Effect of the Invention
[0010] The DNA obtained by the method for obtaining complementary DNA of uracilated DNA of the present invention is excellent in storage stability due to not having uracil, and can be stored with library in the gene reserved. In addition, according to the method of the present invention, DNA can be amplified with converting almost of all non-methylated cytosine into uracil efficiently. As a consequence, detection of methylated cytosine can be performed with a high accuracy.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] [ FIG. 1 ]
[0012] FIG. 1 is the result of electrophoresis carried out for various kinds of
[0013] PCR amplified products. The figure shows, in order from the left, the results of electrophoresis of Nanog gene derived from ES cell and MEF cell in Experimental Example 1, Nanog gene derived from ES cell in Comparative Example 1, Nanog gene derived from MEF cell in Comparative Example 2, Nanog gene derived from ES cell in Example 1, and Nanog gene derived from MEF cell in Example 2, respectively, and the right end shows a marker [(one Step Ladder 100, 0.1-2 kbp (produced by Nippon Gene Co., Ltd.)].
[0014] [ FIG. 2 ]
[0015] FIG. 2 is the result in which various kinds of PCR amplified products were subjected to electrophoresis. The figure shows, in order from the left, the results of electrophoresis of Rex1 gene derived from ES cell and MEF cell in Experimental Example 1, Rex1 gene derived from ES cell in Comparative Example 1, Rex1 gene derived from MEF cell in Comparative Example 2, Rex1 gene derived from ES cell in Example 1, and Rex1 gene derived from MEF cell in Example 2, respectively, and the right end shows a marker [(one Step Ladder 100, 0.1-2 kbp (produced by Nippon Gene Co., Ltd.)].
[0016] [ FIG. 3 ]
[0017] FIG. 3 shows, in order from the left, the results of electrophoresis of CD133 gene derived from ES cell in Example 1, and CD133 gene derived from MEF cell in Example 2, respectively, and the right end shows a marker [(one Step Ladder 100, 0.1-2 kbp (produced by Nippon Gene Co., Ltd.)].
[0018] [ FIG. 4 ]
[0019] In FIG. 4 , “Normal” represents a known nucleotide sequence of Nanog gene (Nucleotide Sequence 13, GenBank Accession No. AC131715), “ES” represents a nucleotide sequence of Nanog gene (Nucleotide Sequence 14) derived from ES cell obtained by the method for detecting methylated cytosine of the present invention, and “MEF” represents a nucleotide sequence of Nanog gene (Nucleotide Sequence 15) derived from MEF cell obtained by the method for detecting methylated cytosine of the present invention, respectively.
[0020] [ FIG. 5 ]
[0021] In FIG. 5 , “Normal” represents a known nucleotide sequence of Rex1 gene (Nucleotide Sequence 16, GenBank Accession No. AC127575), “ES” represents a nucleotide sequence of Rex1 gene (Nucleotide Sequence 17) derived from ES cell obtained by the method for detecting methylated cytosine of the present invention, and “MEF” represents a nucleotide sequence of Rex1 gene (Nucleotide Sequence 18) derived from MEF cell obtained by the method for detecting methylated cytosine of the present invention, respectively.
[0022] [ FIG. 6 ]
[0023] In FIG. 6 , “Normal” represents a known nucleotide sequence of CD133 gene (Nucleotide Sequence 19, GenBank Accession No. AC103621), “ES” represents a nucleotide sequence of CD133 gene (Nucleotide Sequence 20) derived from ES cell obtained by the method for detecting methylated cytosine of the present invention, and “MEF” represents a nucleotide sequence of CD133 gene (Nucleotide Sequence 21) derived from MEF cell obtained by the method for detecting methylated cytosine of the present invention, respectively.
DETAILED DESCRIPTION OF THE INVENTION
[0024] As a single-stranded DNA pertaining to the present invention, a single-stranded DNA containing methylated cytosine is preferable, and the one, which has a promoter region where the content rate of methylated cytosine is high, is preferable. The single-stranded DNA includes unknown sequence and known sequence. In the case of unknown sequence, the nucleotide sequence of the single-stranded DNA before being subjected to the bisulfite reaction has to be analyzed, and therefore, the known sequences is more preferable. The number of base of said single-stranded DNA is usually 50 to 300 bases, preferably 80 to 300 bases, and more preferably it is 100 to 200 bases.
[0025] The single-stranded DNA pertaining to the present invention can be obtained, according to well-known DNA extraction methods such as alkaline SDS method described in, for example, “Labo Manual for Genetic Engineering” (Maruzen Co., Ltd.) and “Handbook of Gene Technology” (Yodosha Co., Ltd.) etc., alternatively, by extracting from a cell, a microorganism, a virus, and the like using a commercially available extraction kit of genomic DNA. It should be noted that, in the case where the extracted DNA is double stranded, single-stranded DNA can be obtained by the well known per se single strand formation treatment.
[0026] Said single strand formation treatment is not limited specifically as long as it is the treatment forming a single strand to be used usually in this field. For example, there are included a heat treatment performed at usually 80 to 100° C., preferably at 80 to 90° C. for usually 30 seconds to 10 minutes, preferably for 1 to 3 minutes, or an alkaline treatment performed by contacting the DNA with alkaline circumstances, etc. Among the above, the alkaline treatment is preferable because the possibility of single-stranded DNA going back to double-stranded is low on the occasion of shifting to the next process. Said alkaline treatment is carried out, specifically for example, by adding alkali or its aqueous solution to the double-stranded DNA or a solution containing the double-stranded DNA to make the solution alkaline of usually pH 10 to pH 14, preferably pH 12 to pH 14. Said alkali includes, for example, alkali metal hydroxide such as sodium hydroxide and potassium hydroxide; alkaline-earth metal hydroxide such as barium hydroxide, magnesium hydroxide, and calcium hydroxide; alkaline metal carbonate such as sodium carbonate; ammonia, and amines and the like. Among them, alkali metal hydroxide such as sodium hydroxide and potassium hydroxide is preferable, and among these, sodium hydroxide is particularly preferable. Said alkaline treatment is performed, more specifically, by adding usually 0.1 to 1 μL, preferably 0.1 to 0.5 μL of 0.5 to 3 mmol/L aqueous alkaline solution to 1 μL of solution including single-stranded DNA, and heating usually for 5 minutes to 60 minutes, preferably for 5 to 30 minutes at usually 25 to 70° C., preferably at 30 to 50° C.
[0027] [A Method for Obtaining DNA which is Complementary to the Single-Stranded DNA in which Non-Methylated Cytosine has been Uracilated (A Method for Obtaining Complementary DNA of Uracilated DNA of the Present Invention)]
[0028] The method for obtaining complementary DNA of uracilated DNA of the present invention is performed by subjecting a single-stranded DNA to 1) bisulfite reaction and 2) reverse transcriptase reaction in sequence. By said method, the DNA, which is complementary to the above-described single-stranded DNA in which non-methylated cytosine has been uracilated, can be obtained easily.
[0029] The above-described bisulfite reaction includes any bisulfite reaction as long as it is the bisulfite reaction which remains methylated cytosine as it is but converts only non-methylated cytosine into uracil and which is usually used in this field. Specifically, for example, the reaction is performed by the following procedure: the single-stranded DNA is reacted with sulfite composition, if need under existence of scavenger, then hydrolyzed, and further, desulfonated under existence of alkali.
[0030] When a single-stranded DNA is provided to the above-described bisulfite reaction, usually it is provided as a solution which dissolves the single-stranded DNA, and said solution includes the one dissolved, for example, in Good's buffer solution such as MES and HEPES, phosphate buffer solution, Tris buffer solution, glycine buffer solution, borate buffer solution, sodium bicarbonate buffer solution, and sterile water, etc., having pH 6 to 8; and among them, the one dissolved in sterile water is preferable. The amount of single-stranded DNA in said solution is not limited specifically, but usually it is 10 to 100 ng in 1 to 10 μL of the solution.
[0031] The sulfites in the reaction of single-stranded DNA with sulfite composite in the above-described bisulfite reaction includes, for example, sodium bisulfite and ammonium sulfite, and, sodium bisulfite is preferable. The usage thereof is one so that the final concentration in the reaction solution gives 1 to 6 mol/L relative to usually 1 to 500 μL of a solution including 50 ng to 500 ng of single-stranded DNA. The scavenger described above includes, for example, hydroquinone compounds such as hydroquinone and the like. Said scavenger may be added so that the final concentration gives 1 to 5 mmol/L relative to 1 to 500 μL of a solution including 500 ng to 5 μg of single-stranded DNA. The reaction of said single-stranded DNA with sulfite is performed usually by making react at 30 to 70° C., preferably at 40 to 60° C., more preferably at 50 to 60° C., and usually for 40 minutes to 24 hours, preferably for 1 hour to 20 hours, more preferably for 4 μL hours to 16 hours.
[0032] The hydrolysis during the above-described bisulfite reaction is not limited specifically as long as it is a method usually performed in this field, and it is performed usually by heating at 30 to 70° C., preferably at 40 to 60° C., and usually for 40 minutes to 24 hours, preferably for 1 hour to 20 hours, more preferably for 4 μL hours to 16 hours. It should be noted that said hydrolysis treatment may be carried out simultaneously with the above-described reaction of single-stranded DNA with the sulfite.
[0033] It should be noted that, with respect to the single-stranded DNA which carried out the above-described hydrolysis, it is preferable to subject it to purification treatment before desulfonation treatment. Said purification treatment is the treatment to be carried out for removing high-concentration of sulfite salt to be used in the bisulfite reaction, and it may be carried out according to the method for purifying DNA to be carried out usually in this field. Specifically, there are included for example, a method in which chaotropic agent such as guanidine hydrochloride or sodium iodide is added to the single-stranded DNA or a solution including single-stranded DNA, and it is separated and purified by HPLC method etc.; for example, extraction and purification by a mixed solution of phenol/chloroform/isoamyl alcohol; alcohol precipitation method; purification by a column filled with silica gel; filtration method with filter, etc.;
[0034] among them, the alcohol precipitation method is preferable. Said alcohol precipitation method is specifically performed as follows.
[0035] That is, to a 10 μL of solution including single-stranded DNA after hydrolysis, usually, 40 to 110 μL of alcohol and 30 to 100 μL of buffer solution are added, and centrifugal separation is carried out. After centrifugal separation, by removing supernatant and washing with alcohol, objective single-stranded DNA can be separated and purified. At the time when the above-described alcohol and buffer solution are added, to facilitate removal of supernatant after separation, 0.1 to 1 μL of Ethachinmate or glycogen may be added to 10 μL of the solution including single-stranded DNA. The above-described alcohol includes ethanol, isopropanol, and butanol, and the like; and, isopropanol is particularly preferable.
[0036] In the bisulfite reaction pertaining to the present invention, although the reason is unclear, when isopropanol is used, only the objective single-stranded DNA can be precipitated efficiently and it will become possible to advance the reaction efficiently. The above described buffer solution includes, for example, Good's buffer solution such as MES and HEPES, phosphate buffer solution, Tris buffer solution, glycine buffer solution, borate buffer solution, and sodium bicarbonate buffer solution and so on; among them, Good's buffer solution such as MES and HEPES, Tris buffer solution, etc. are preferable, and Tris buffer solution is particularly preferable. The pH of these buffer solutions is usually 7 to 8, preferably 7 to 7.5, and concentration of buffer agent in the buffer solution is usually in the range of 0.1 to 5 mol/L, preferably 0.1 to 2 mol/L. The above-described centrifugal separation is not limited specifically as long as it is an aspect to be carried out usually in this field, and usually it is carried out by 10,000 g to 22,000 g for 10 to 30 minutes.
[0037] The desulfonation reaction in the above-described bisulfite reaction includes the same method as alkaline treatment in the section of the above-described single strand formation treatment, and a preferable aspect also includes the same one.
[0038] The reverse transcriptase reaction is usually employed in this field for synthesizing complementary strand DNA through the use of reverse transcriptase activity (reverse-transcription reaction activity: RNA-dependent DNA polymerase activity) which the reverse transcriptase has, and using single-stranded RNA as a template. However, in the present invention, the reverse transcriptase reaction is employed for synthesizing complementary strand DNA through the use of DNA-dependent DNA polymerase activity which the reverse transcriptase has, and using single-stranded DNA as a template. That is, the reverse transcriptase reaction in the present invention may be carried out according to the method for synthesizing complementary strand DNA by employing well known per se single-stranded RNA, which is usually used in this field, except for employing single-stranded DNA instead of single-stranded RNA as a template. The above-described single-stranded DNA, which carried out the bisulfite reaction pertaining to the present invention, (hereinafter, sometimes abbreviated as DNA after bisulfite reaction) may be subjected to the reverse transcriptase reaction, and may also be carried out using commercially available kit. Specifically, for example, to 1 μg quantity of nucleic acid of the DNA after bisulfite reaction, usually 50 to 500 Units, preferably 100 to 400 Units of reverse transcriptase, usually 0.1 to 1 μg, preferably 0.5 to 1 μg of primers for reverse transcriptase reaction, usually each 1 to 50 nmol, preferably 1 to 20 nmol of 4 μL kinds of deoxyribonucleotide triphosphate (dNTPs) are added, and reacted in a buffer solution (pH 7 to pH 8.5) such as Tris hydrochloric acid buffer solution, HEPES, and MOPS buffer solution, preferably a buffer solution (pH 8 to pH 8.5) such as Tris buffer solution and HEPES buffer solution, at usually 35 to 50° C., preferably at 40 to 50° C. for usually 30 to 90 minutes, preferably for 30 to 60 minutes. Thereby, a single-stranded DNA, which is complementary to the DNA after bisulfite reaction, can be obtained. It should be noted that, in the case where the primer is random primer, it is necessary to advance annealing reaction before carrying out the above-described reaction. Therefore, when the reaction is carried out using random primer, after adding the above-described amount of reverse transcriptase, random primer, and 4 μL kinds of deoxyribonucleotide triphosphate (dNTPs) to the DNA after bisulfite reaction, annealing reaction is carried out usually at 20 to 40° C., preferably at 20 to 30° C. for 5 to 30 minutes, preferably for 10 to 20 minutes, after that, the reverse transcriptase reaction is carried out at the above-described temperature for the above-described time.
[0039] It should be noted that, in the above-described reverse transcriptase reaction, it is preferable to stop the reaction by heating treatment or by adding reaction stop solution, after reaction. Said heat treatment is carried out usually at 65 to 100° C., preferably at 65 to 70° C. for usually 15 to 60 minutes, preferably for 15 to 30 minutes. In addition, the reaction stop solution includes, for example, EDTA and the like, and its usage is one to provide final concentration to be usually 10 to 100 mmol/L, preferably 40 to 60 mmol/L.
[0040] In addition, in the above-described reverse transcriptase reaction, regents such as reducing agent of DTT (dithiothreitol) etc., potassium chloride, magnesium chloride, which are usually used at such reverse transcriptase reaction, may be added. Concentration and usage of these reagents may be selected appropriately from the range usually employed in this field.
[0041] The reverse transcriptase at the above-described reverse transcriptase reaction is not limited specifically as long as it has a DNA dependent DNA polymerase activity, which includes, for example, Moloney Murine Leukemia Virus (M-MLV) reverse transcriptase, Avian myeloblastosis virus (AMV) reverse transcriptase, and M-MLV reverse transcriptase (RNase H Minus);and, M-MLV reverse transcriptase (RNase H Minus) is preferable among them.
[0042] The primer for reverse transcriptase reaction may be the one which can anneal to DNA after bisulfite reaction, which becomes a template, and serves as a starting point of DNA chain extension. Number of nucleotides of the primer for reverse transcriptase reaction is usually 6 to 12 mer, preferably 6 to 10 mer, more preferably 6 to 9 mer. It should be noted that, when the single-stranded DNA pertaining to the present invention is unknown, it is preferable to use this random primer.
[0043] The above-described dNTPs is not limited specifically as long as it is a mixture of four kinds of deoxyribonucleotide triphosphate (dATP, dCTP, dGTP, dTTP) usually employed in this field.
[0044] A preferable example of the method for obtaining complementary DNA of uracilated DNA of the present invention will be explained below.
[0045] That is, for example, DNA is extracted from cell and the like using a DNA extraction kit and the like, then 1 μg of DNA is dissolved, for example, in sterile water to prepare a solution including DNA. When the obtained DNA is double-stranded DNA, to 3 to 5 μL of the solution including DNA, for example, 1 μL to 5 μL of 1 to 3 mol/L sodium hydroxide etc. is added, and reacted at 30 to 50° C. for 10 to 30 minutes to make the DNA single strand.
[0046] After that, to 4 μL to 8 μL of a solution including the obtained single-stranded DNA, 30 to 50 μL of 2 to 3 mol/L sodium bisulfite, and if need, 3 to 5 μL of 20 to 50 mmol/L hydroquinone are added, and heated at 80 to 90° C. for 60 to 100 minutes. By reacting under said condition, cytosine in the single-stranded DNA is sulfonated, and at the same time, the sulfonated cytosine can be hydrolyzed. Subsequently, 5 to 10 times larger volume than the post-hydrolysis solution of 1 mol/L Tris buffer solution (pH 7.5 to 8.0) and isopropanol are added by a ratio of 40:60 to 60:40, preferably by a ratio of 40:60 to 50:50, respectively, to precipitate the single-stranded DNA after hydrolysis. On this occasion, when 1 to 3 μL of Ethachinmate is added, confirmation of DNA precipitation will become easy.
[0047] After that, centrifugal separation is carried out by 10,000 to 20,000 g for 10 to 20 minutes and then removes the supernatant, and the obtained DNA is washed with ethanol. Thereby, the single-stranded DNA after hydrolysis can be extracted and purified. Furthermore, 1 μg of the obtained single-stranded DNA is dissolved, for example, in 30 to 40 μL of sterile water, and to said solution, 5 to 20 μL of 1 to 3 mol/L sodium hydroxide is added and reacted at 30 to 40° C. for 20 to 60 minutes to desulfonate. After that, if need, the purification is performed by removing low molecular weight DNA using a commercially available kit, etc. Thereby, the bisulfite reaction is completed, and single-stranded DNA, in which non-methylated cytosine has been uracilated efficiently, can be obtained.
[0048] Next, to 5 to 10 μL of a solution containing 1 μg of single-stranded DNA obtained by bisulfite reaction, for example, 1 to 2 μg of 1 to 3 μg/μL random primers (5 to 15 mer), 1 to 2 μg, of 100 to 400 Units reverse transcriptase, and 5 to 10 μg of mixed solution of 1 to 3 mmol/L of 4 μL kinds of deoxyribonucleotide triphosphate (dNTPs) are added; and annealing reaction is performed usually at 20 to 40° C. for 10 to 20 minutes; after that, by carrying out extension reaction with reacting at 37 to 50° C. for usually 30 to 60 minutes, reverse transcriptase reaction is carried out. After the reaction, the obtained single-stranded DNA is purified by removing low molecular weight DNA using, for example, commercially available kit, etc.
[0049] By the above-described procedure, the DNA, which is complementary to single-stranded DNA in which non-methylated cytosine has been uracilated (hereinafter, sometimes abbreviated as a complementary DNA of uracilated DNA) can be obtained.
[0050] [A Method for Amplifying DNA which is Complementary to Single-Stranded DNA in which Non-Methylated Cytosine has been Uracilated (A Method for Amplifying Complementary DNA of Uracilated DNA of the Present Invention)]
[0051] The method for amplifying complementary DNA of uracilated DNA of the present invention can amplify efficiently the DNA, which is complementary to the above-described single-stranded DNA in which non-methylated cytosine has been uracilated, by subjecting single-stranded DNA to 1) bisulfite reaction, 2) reverse transcriptase reaction and 3) PCR reaction in this order.
[0052] As for the above-described bisulfite reaction and reverse transcriptase reaction, the same method as described in a section of the method for obtaining complementary DNA of uracilated DNA of the present invention is included, and the preferable condition, etc. are also the same.
[0053] The PCR reaction in the method for amplifying complementary DNA of uracilated DNA of the present invention may be carried out according to the method well known per se, for example, the method described in Nucleic Acids Research, 1991, Vol. 19, 3749, BioTechniques, 1994, Vol. 16, 1134-1137, and specifically, is carried out as follows. That is, to 1 to 100 ng of quantity of nucleic acid of single-stranded DNA (herein after, sometimes abbreviated as post-reverse-transcriptase reaction DNA), which becomes a template, obtained by the above-described reverse transcriptase reaction, usually 0.1 to 100 pmol, preferably 0.1 to 50 pmol of 2 kinds of primers, respectively, usually 1 to 10 Units, preferably 2.5 to 5 Units of DNA polymerase, and usually 0.01 to 20 μtmol, preferably 0.01 to 10 μtmol of a mixture of 4 μL kinds of deoxyribonucleotide triphosphate (dNTPs) are added. By setting, for example, the processes of (1) 93 to 98° C. for 1 to 10 minutes→(2) 93 to 98° C. for 10 to 30 seconds→(3) 50 to 60° C. for 10 to 30 seconds→(4) 68 to 72° C. for 30 seconds to 5 minutes as 1 cycle, and by carrying out for 20 to 40 cycles in a buffer solution such as Tricine buffer solution and Tris buffer solution, etc., the DNA complementary to the DNA after bisulfite reaction can be amplified and obtained. In the above-described PCR reaction, after the reaction, it is preferable to purify the obtained DNA by purification method to be used usually in this field, such as, for example, extraction by a mixed solution of phenol/chloroform/isoamyl alcohol, alcohol precipitation, column purification, filtration by a filter, etc. In addition, after the above-described purification, it is more preferable to extract DNA having objective base pair (bp). Said extraction method includes the method well known per se, for example, the method using agarose gel electrophoresis, the method using liquid chromatography, and the method using electrophoresis on polyacrylamide gel and the like as described in Labo Manual for Genetic Engineering, Expanded Edition. In addition, the double-stranded DNA pertaining to the present invention which is obtained by the above-described PCR reaction may be subjected to further PCR reaction to obtain more amount of objective
[0054] DNA.
[0055] Two kinds of primers in the above-described PCR reaction is the one which includes a part of DNA after reverse-transcriptase reaction and the one which includes a part of complementary strand of DNA after reverse-transcriptase reaction, which is a template, and number of nucleotides thereof is usually 12 to 40, preferably 15 to 35, more preferably 18 to 30.
[0056] The DNA polymerase in the above-described PCR reaction may be any DNA polymerase as long as it is usually used in this field, and, the one which has 3′→5′ exonuclease activity is preferable. Specifically, α-type DNA polymerase such as, for example, Pfu DNA polymerase, KOD DNA polymerase is preferable, among them, the KOD DNA polymerase is particularly preferable. By using such DNA polymerase having 3′→5′ exonuclease activity, it becomes possible to amplify accurately the DNA complementary to the DNA after bisulfite reaction, as a consequence, highly accurate detection of methylated cytosine becomes possible.
[0057] The above-described dNTPs is not limited especially if it is a mixture of 4 μL kinds of deoxyribonucleotide triphosphate (dATP, dCTP, dGTP, dTTP) usually employed in this field.
[0058] A preferable example of the method for amplifying complementary DNA of uracilated DNA of the present invention is explained below.
[0059] That is, first, as described in the section of the method for obtaining complementary DNA of uracilated DNA of the present invention, by subjecting a single-stranded DNA to bisulfite reaction and reverse transcriptase reaction in this order, the complementary DNA of uracilated DNA is obtained. After that, the obtained DNA is subjected to the PCR reaction. That is, to 1 to 3 μL of a solution including 100 ng to 1 μg of single-stranded DNA obtained by the reverse transcriptase reaction, 5 to 10 μL of 1 to 10 μmol/L primer for upstream of the DNA of amplification target and 5 to 10 μg of 1 to 10 μmol/L primer for downstream of the DNA of amplification target, 5 to 10 μg of a mixture of 4 μL kinds of 1 to 5 mmol/L deoxyribonucleotide triphosphate (dNTPs), and 20 to 30 μg of 1 to 5 Units KOD DNA polymerase are added. Next, for example, by setting the reactions at 93 to 98° C. for 1 to 10 minutes→93 to 98° C. for 10 to 30 seconds→50 to 60° C. for 10 to 30 seconds→68 to 72° C. for 30 seconds to 5 minutes as 1 cycle, 20 to 40 cycles of reaction are carried out. Thereby, the DNA complementary to a DNA, in which non-methylated cytosine has been uracilated, is amplified. After that, said double-stranded DNA is subjected to electrophoresis with using, for example, agarose gel or nondenaturing polyacrylamide gel, and DNA of desired chain length is extracted. It should be noted that, if need, the obtained DNA may be purified for example, by extraction with a mixed solution of phenol/chloroform/isoamyl alcohol. By the above procedure, the complementary DNA of uracilated DNA can be amplified.
[0000] [A method for Detecting Methylated Cytosine of the Present Invention]
[0060] The method for detecting methylated cytosine of the present invention is performed by subjecting single-stranded DNA to 1) bisulfite reaction, 2) reverse transcriptase reaction and 3) PCR reaction in this order, and by carrying out nucleotide sequence analysis of the obtained PCR amplification product
[0061] In the method for detecting methylated cytosine of the present invention, bisulfite reaction, reverse transcriptase reaction, and PCR reaction are the same methods as described in a section of the method for obtaining complementary DNA of uracilated DNA of the present invention and the method for amplifying complementary DNA of uracilated DNA of the present invention, and the preferable condition, etc. are also the same.
[0062] As the above-described nucleotide sequence analysis, there is no particular limitation as long as it is a method for analyzing nucleotide sequence usually employed in this field. For example, it may be carried out according to a routine procedure such as a fluorescent dye terminator sequencing method and Sanger's method which are described in Lab Manual for Genetic Engineering, and Handbook of Gene Technology, etc. Specifically, for example, a complementary DNA of uracilatd DNA, which is obtained by the amplification method of the present invention, is incorporated in a vector; and the obtained recombinant vector is transfected into competent cell; said competent cell is cultured; and from there, a plasmid including complementary DNA of uracilated DNA is extracted; and using said plasmid, decoding is performed by, for example, a sequencer and the like. By comparing thus obtained nucleotide sequence with the nucleotide sequence of normal DNA which has not been subjected to the bisulfite reaction, methylated cytosine can be detected. That is, in the bisulfite reaction pertaining to the present invention, since all cytosine except for methylated cytosine are converted into uracil, the methylated cytosine can be detected by finding out cytosine not converted into uracil in the obtained nucleotide sequence.
[0063] The method for incorporating the above-described complementary DNA of uracilated DNA into a vector includes, specifically, for example, a method for inserting complementary DNA of uracilated DNA into a vector using T4 μL DNA ligase after the vector such as plasmid, cosmid, and phagemid, and complementary DNA of uracilated DNA are blunt-ended by T4 μL DNA polymerase and the like, or a TA cloning method, in which adenine (A) is added to the complementary DNA of uracilated DNA, and said adenine-added complementary DNA of uracilated DNA is incorporated into a thymine base- added vector, using T4 μL DNA ligase. Among them, the TA cloning method is preferable because it does not require cleaving both DNA to be inserted and vector by restriction enzyme, and it is simple.
[0064] Said TA cloning method is carried out, specifically, for example as follows. That is, to 100 ng of the complementary DNA of uracilated DNA after PCR reaction, 1 to 5 Units of Taq DNA polymerase is added, and reacted at 55 to 75° C. for 10 to 30 minutes, and adenine is added to 3′-terminal of the complementary DNA of uracilated DNA. It should be noted that, on the occasion of said reaction, 0.01 to 20 nmol of dATP relative to 1 μg of the complementary DNA of uracilated DNA may be added to the reaction solution, however, by adding Tag DNA polymerase to the PCR reaction solution, this addition step can be skipped. In addition, with respect to the complementary DNA of the adenine-added uracilated DNA, after synthetic reaction, it is preferable to purify the obtained DNA by a method such as extraction with a mixed solution of phenol/chloroform/isoamyl alcohol, alcohol precipitation, column purification, and filtration by a filter, etc. Subsequently, to 10 to 100 ng of complementary DNA of the adenine-added uracilated DNA, thymine base-added vector for E. coli transformation and 300 to 3000 Units of T4 μL DNA ligase are added, and by reacting at 10 to 40° C. for 30 to 90 minutes, a recombinant vector, in which the complementary DNA of uracilated DNA is incorporated, can be obtained.
[0065] A method for transforming the above-described recombinant vector to competent cell includes, for example, a heat shock method by heating at 35 to 45° C. for 20 to 90 minutes, and an electroporation method in which 1.5 to 2.5 kV of electric pulse is applied, but the electroporation method is more preferable. As the competent cell to be used herein, if it is E. coli or B. subtilis , which is usually used, any one of them can be employed, and its usage to be used may be set appropriately within the range usually employed.
[0066] Cultivation of the above-described competent cell is performed, for example, on a medium such as LB agar medium including 30 to 150 μg/mL of ampicillin, or M9 agar medium including 30 to 150 μg/mL of ampicillin, at 30 to 40° C. for 12 to 20 hours. It should be noted that, as the above-described medium, either one of natural medium or synthetic medium etc. may be employed as long as it contains carbon source, nitrogen source and inorganic salts, which become nutritional source of bacteria, and yeast extract as a growth factor, and it enables to culture the transformant efficiently. Said carbon source includes carbohydrates such as glucose, fructose, sucrose and starch; organic acids such as acetic acid and propionic acid, and alcohols such as ethanol and propanol. Said nitrogen source includes ammonia; ammonium salt of inorganic acid or organic acid such as ammonium chloride, ammonium sulfate, ammonium acetate, and ammonium phosphate; or other nitrogen-containing compounds, in addition, peptone, tryptone, meat extract, and Corn Steep Liquor, and the like. The inorganic salts include monobasic potassium phosphate, dibasic potassium phosphate, magnesium phosphate, magnesium sulfate, sodium chloride, ferrous sulfate, manganese sulfate, copper sulfate, and calcium carbonate, etc.
[0067] As a method for extracting the plasmid including the complementary DNA of uracilated DNA from cultured competent cell, for example, first, the DNA derived from plasmid, which includes the complementary DNA of uracilated DNA in a colony is amplified by colony PCR method. After that, may be carried out whether the objective plasmid is amplified in a colony is determined, for example, by electrophoresis, and from the colony, which is identified insertion of objective plasmid, the objective plasmid is extracted.
[0068] Said colony PCR method is carried out, for example, as follows. That is, to the cultured colony, usually 0.1 to 100 pmol, preferably 0.1 to 50 pmol of 2 kinds of PCR primers for detection of objective nucleotide sequence, respectively, usually 0.01 to 20 nmol, preferably 0.01 to 10 nmol of 4 μL kinds of mixed deoxyribonucleotide triphosphate (dNTPs), and usually 1 to 10 Units, preferably 1 to 5 Units of DNA polymerase are added, and in a buffer solution such as Tricine buffer solution, Tris hydrochloric acid buffer solution and the like, and for example, by setting the reactions (1) at 93 to 98° C. for 1 to 10 minutes→(2) at 93 to 98° C. for 10 to 30 seconds→(3) at 50 to 60° C. for 10 to 30 seconds→(4) at 68 to 72° C. for 30 seconds to 5 minutes as 1 cycle, 25 to 40 cycles of reaction are carried out. The above-described 2 kinds of primer include the one which is designed to be able to amplify the objective DNA. That is, the one which includes the entire or a part of uracilated DNA and the one which includes the entire or a part of the complementary DNA of uracilated DNA, or the sequences derived from vector which locate at both end of the inserted complementary DNA of uracilated DNA, and, the sequences derived from vector, which locate in the both end of the complementary DNA of uracilated DNA, are preferable. That is, in the method of the present invention, since non-methylated cytosine is uracilated, and said uracil is read as thymine at the time of reverse transcriptase reaction, if all cytosine were non-methylated cytosine, the complementary DNA of uracilated DNA would be consisted of 3 nucleotides. Therefore, in order to carry out the PCR reaction efficiently, the sequence of the vector origin located in the both ends of the complementary DNA of uracilated DNA, which can be constituted by 4 μL nucleotides, is preferable as the primer. The number of nucleotides of the above-described primer is usually 12 to 30, preferably 15 to 25, more preferably 18 to 22. The above-described DNA polymerase may be any DNA polymerase as long as it is usually employed in this field, and specifically, for example, there are included Taq DNA polymerase, Tth DNA polymerase, and KOD DNA polymerase, etc., and among them, Taq DNA polymerase and KOD DNA polymerase, etc. are preferable.
[0069] The electrophoresis method to be carried out after the above-described colony PCR reaction may be any electrophoresis method, which is usually employed in this field, as long as it can determine the number of nucleotides from the mobility; however agarose gel electrophoresis method is preferable. It should be noted that, the electrophoretic condition in said electrophoresis method may be set appropriately according to well-known method.
[0070] As the method for taking out plasmid from the above-described colony part, plasmid may be extracted by well-known plasmid extraction method such as alkaline SDS method, after shaking culture, for example, described in Lab Manual for Genetic Engineering (Maruzen Co., Ltd.), and Handbook of Gene Technology (Yodosha Co., Ltd.). It should be noted that, extraction of plasmid may be carried out using commercially available kit. As the culture medium in the above-described shaking culture, the same medium as described in the section of cultivation of competent cell can be used except for making solution without using agarose, and preferable cultivation time and cultivation temperature are also the same range as described in the section of cultivation of competent cell.
[0071] Preferable example of the method for detecting methylated cytosine of the present invention is explained below.
[0072] That is, first, as descried in the sections of the method for obtaining complementary DNA of uracilated DNA of the present invention and the method for amplifying complementary DNA of uracilated DNA of the present invention, by subjecting single-stranded DNA to bisulfite reaction, reverse transcriptase reaction, and PCR reaction in this order, the complementary DNA of uracilated DNA is obtained. To 5 μg to 10 μL of a solution including 100 ng to 1 μg of said complementary DNA of uracilated DNA, 0.5 to 1 μL of 1 to 5 Units of Taq DNA polymerase are added, and reacted at 55 to 75° C. for 10 to 30 minutes to add adenine to 3′-terminal of the complementary DNA of uracilated DNA. It should be noted that, with respect to the adenine-added complementary DNA of uracilated DNA, after synthetic reaction, it is preferable subject it to purification process. Next, to 1 to 5 μg of sterile water including 10 to 100 ng of the adenine-added complementary DNA of uracilated DNA, 1 to 3 μL of 10 to 100 ng of a thymine-added vector for E. coli transformation, and 1 to 3 μL of 300 to 3000 Units of T4 μL DNA ligase are added, and reacted at 10 to 20° C. for 30 to 240 minutes to obtain a recombinant vector incorporated with the complementary DNA of uracilated DNA. After that, 10 to 100 ng of the obtained recombinant vector is added to 10 8 to 10 9 cells of competent cell, and transformation is performed by applying 1.5 to 2.5 kV of electric pulse. Furthermore, cells are cultured, for example, on agar medium including 30 to 150 μg/mL of ampicillin, 1% (w/v) of tryptone, 0.5% (w/v) of yeast extract, and 1% (w/v) of sodium chloride at 30° C. to 40° C. for 12 hours to 20 hours. Next, the obtained culture is subjected to the colony PCR. Specifically, to 1 μg to 10 μg of sterile water dissolved colony, 1 to 10 μmol/L of 2 kinds of primers, which are designed to be able to amplify the objective DNA, respectively, usually 1 to 5 μL of 1 to 10 mmol/L of 4 μL kinds of mixed deoxyribonucleotide triphosphate (dNTPs) and 0.5 to 1 μg of 1 to 5 Units Taq DNA polymerase are added, and reacted in a buffer solution such as Tricine buffer solution and Tris hydrochloric acid buffer solution, and by setting the reaction (1) at 93 to 98° C. for 1 to 10 minutes→(2) at 93 to 98° C. for 10 to 30 seconds→(3) at 50 to 60° C. for 10 to 30 seconds→(4) at 68 to 72° C. for 30 seconds to 5 minutes as 1 cycle, 25 cycles to 40 cycles of reaction are carried out. After that, existence of the objective DNA in the colony is determined by agarose gel electrophoresis, and identified colonies are collected. After carrying out shaking culture of the collected colonies in LB medium, the objective DNA is taken out from the culture medium using, for example, commercially available plasmid extraction kit and the like, and nucleotide sequence of the DNA is decoded by a sequencer, etc. Comparing the obtained sequence with the normal nucleotide sequence which is not subjected to the bisulfite reaction, and by finding out the cytosine which is not uracilated in the decoded nucleotide sequence, the methylated cytosine can be detected.
[0073] Hereinafter, the present invention will be explained in more detail by referring to Experimental Example, Examples, and Comparative Examples and so on, however, the present invention is not limited thereto in any way.
EXAMPLE
Experimental Example 1: Extraction of Mouse Genomic DNA
[0074] Using QuickGene SP kit DNA tissue (produced by Fuji Film Co., Ltd.), from 1×10 6 cells of mouse embryonic stem cell (ES cell) and mouse embryonic fiblobrast cell (MEF cell), genomic DNA was extracted according to an attached instruction manual.
[0075] Then, confirmation of presence of ES cell-derived Nanog gene and Rex1 gene, and MEF cell-derived Nanog gene and Rex1 gene was carried out.
[0076] That is, sterile water was added to each 10 μg of the obtained purified mouse genomic DNA derived from ES cell and MEF cell so as to give the total volume 33.5 μL. Two kinds of these solutions were prepared, and the PCR amplification was carried out for promoter region of mouse Nanog gene and Rex1 gene. That is, to the above-described sterile water, 5 μL of 10×Gene Taq Universal Buffer (produced by Nippon Gene Co. Ltd.), 5 μL of dNTPs mixed solution (2.5 mmol/each) (produced by Nippon Gene Co. Ltd.), and 0.5 μL, of Gene Taq NT (produced by Nippon Gene Co. Ltd.) were added, and to this solution, 3 μL of 5 μmol/L of PCR primer Forward solution and Reverse solution for Nanog gene [Forward: 5′ CTGTGAATTCACAGGGCTGGTGGG 3′ (Nucleotide sequence 1), Reverse: 5′CAACCAAATCAGCCTATCTGAAGGCC 3′ (Nucleotide sequence 2)], respectively, or 3 μg of 5 μmol/L PCR primer Forward solution and Reverse solution for Rex1 gene [Forward: 5′ GGGTCACCTGAAGGGCCAGGGGCC 3′ (Nucleotide sequence 3), Reverse: 5′ CTTGGACCCCTCCCTTTTTAGATGG 3′ (Nucleotide sequence 4)], respectively, were added to make the total volume 50 μL, and by setting the reactions at 95° C. for 2 minutes, at 95° C. for 20 seconds, and at 68° C. for 30 seconds as 1 cycle, 30 cycles of PCR reaction were carried out. After that, the obtained respective PCR amplified products were electrophoresed using 1.5% agarose gel, and the presence of ES cell derived Nanog gene and Rex1 gene, and MEF cell derived Nanog gene and Rex1 gene were confirmed.
[0077] The result of Nanog gene was shown in FIG. 1 , and the result of Rex1 gene was shown in FIG. 2 . From said results, the presence of Nanog gene and Rex1 gene could be confirmed in both ES cell and MEF cell.
Example 1
Uracilation of Non-Methylated Cytosine in the ES Cell-Derived Nanog Gene, ES Cell-Derived Rex1 Gene, and ES Cell-Derived CD133 Gene by the Method of the Present Invention
(1) Single Strand Formation of Genomic DNA by Alkaline Treatment
[0078] One μg of ES cell-derived genomic DNA obtained in Example 1 was placed in a tube, and 3 tubes were prepared as a tube for Nanog gene, a tube for Rex1 gene, and a tube for CD133 gene. After each of these was adjusted to 4.5 μg by adding sterile water, 2 μL of 1 mol/L sodium hydroxide (produced by Wako Pure Chemical Industries Co., Ltd.) was added to make the total volume 6.5 μL, and incubated at 37° C. for 20 minutes to make each genomic DNA single stranded.
(2) Bisulfite Reaction
[0079] To 6.5 μL of the solution including single-stranded genomic DNA in each three tubes, 3.5 μL of 30 mmol/L hydroquinone (produced by Wako Pure Chemical Industries Co., Ltd.), 40 μL of 2.5 mol/L sodiumhydrogensulfite (produced by Wako Pure Chemical Industries Co., Ltd.) were added to make the total volume 50 μL, and incubated at 55° C. for 16 hours. Then, 350 μL of 1 mol/L Tris buffer solution (pH 7.5) (produced by Nippon Gene Co., Ltd.), 1 μL of Ethachinmate (produced by Nippon Gene Co., Ltd.), and 400 μL of isopropanol (produced by Wako Pure Chemical Industries Co., Ltd.) were added, respectively, and centrifugal separation was carried out by 18800×g for 10 minutes. After that, the supernatant was removed and washed with 75% ethanol (produced by Wako
[0080] Pure Chemical Industries Co., Ltd.), and then, sterile water was added to make the total volume 35 μL.
[0081] Next, to 35 μL of the solution containing genomic DNA in each three tubes, 15 μL of 1 mol/L sodium hydroxide (produced by Wako Pure Chemical Industries Co., Ltd.) was added to make the total volume 50 μL, and incubated at 37° C. for 20 minutes, and thus the desulfonation reaction was performed. Then, 12 μL of 10 mol/L ammonium acetate (produced by Nippon Gene Co., Ltd.) and 125 μL of ethanol (produced by Wako Pure Chemical Industries Co., Ltd.) were added, respectively, and centrifugal separation was carried out by 18800×g for 10 minutes. Subsequently, the supernatant was removed and washed with 75% ethanol (produced by Wako Pure Chemical Industries Co., Ltd.), and then, sterile water was added so as to adjust the total volume 50 μL. After that, using QIAquick PCR Purification Kit (QIAGEN, Inc.), low molecular weight DNA was removed according to an attached instruction manual. Furthermore, to the solution after removal procedure, 1 μL of Ethachinmate (produced by Nippon Gene Co., Ltd.), 5 μL of 3 mol/L sodium acetate (produced by Nippon Gene Co., Ltd.), and 125 μL of ethanol (produced by Wako Pure Chemical Industries Co.,
[0082] Ltd.) were added, respectively, and centrifugal separation was carried out by 18800×g for 10 minutes. Finally, the supernatant was removed and washed with 75% ethanol (produced by Wako Pure Chemical Industries Co., Ltd.), and then sterile water was added so as to make the total volume 6 μL.
(3) Reverse Transcriptase Reaction
[0083] To each 6 μL of solution containing genomic DNA after bisulfite reaction in the 3 tubes, 1 μL of random primer (6 mer, 1 μg/μL) (produced by Takara Bio Inc.) was added to make the total volume 7 μL; and after the solution was incubated at 90° C. for 1 minute, and cooled down immediately with ice, and thus heat denaturation was performed. After that, 4 μL μg of 5×buffer (produced by TOYOBO Co. Ltd.), 8 μL of 2.5 mmol/L dNTPs mixed solution (produced by Nippon Gene Co. Ltd.), and 1 μg of ReverTra Ace (produced by TOYOBO Co. Ltd.) were added, respectively, to make the total volume 20 μL, and after incubation at 25° C. for 10 minutes, by performing incubation at 42° C. for 30 minutes, elongation reaction by reverse transcriptase was carried out. Subsequently, using QIAquick PCR Purification Kit (QIAGEN, Inc.), low molecular weight DNA was removed according to an attached instruction manual. After that, to the solution after removal treatment of low molecular weight DNA, 1 μL of Ethachinmate (produced by Nippon Gene Co., Ltd.), 5 μg of 3 mol/L sodium acetate (produced by Nippon Gene Co., Ltd.), and 125 μL of ethanol (produced by Wako Pure Chemical Industries Co., Ltd.) were added, respectively, and centrifugal separation was carried out by 18800×g for 10 minutes. Further, the supernatant was removed and washed with 75% ethanol (produced by Wako Pure Chemical Industries Co., Ltd.), and then sterile water was added so as to make the total volume 10 μL.
(4) PCR Reaction
[0084] To each 1 μL of a solution containing genomic DNA in 3 tubes which was performed reverse transcriptase reaction, 7 μL of sterile water, 25 μL of 2×PCR buffer for KOD FX (produced by TOYOBO Co. Ltd.), 10 μL of 2.5 mmol/L dNTPs mixed solution (produced by TOYOBO Co. Ltd.), and 1 μL of KOD FX (produced by TOYOBO Co. Ltd.) were added, and to this solution each 3 μL of 5 μmol/L PCR primer Forward solution and Reverse solution for Nanog gene [Forward: 5′ TTGTGAATTTATAGGGTTGGTGGG 3′ (Nucleotide sequence 5), Reverse: 5′ CAACCAAATCAACCTATCTAAAAACC 3′ (Nucleotide sequence 6)], each 3 μL of 5 μmol/L PCR primer Forward solution and Reverse solution for Rex1 gene
[0085] [Forward: 5′ GGGTTATTTGAAGGGTTAGGGGTT 3′ (Nucleotide sequence 7), Reverse: 5′ CTTAAACCCCTCCCTTTTTAAATAA 3′(Nucleotide sequence 8)], or each 3 μL of 5 μmol/L PCR primer Forward solution and Reverse solution for CD133 gene [Forward: 5′ GTTTTTTAAATTATTGAGTTTTGTGGAG 3′ (Nucleotide sequence 9), Reverse: 5′ CACCACAAAAATAATTAAATAAAAACCC 3′ (Nucleotide sequence 10)] were added to make the total volume 50 μL, and by setting the reaction at 94° C. for 2 minutes→at 98° C. for 10 seconds→at 55° C. for 20 seconds→at 68° C. for 30 seconds as 1 cycle, 35 cycles of PCR reaction were carried out. After that, the obtained respective PCR amplified products were fractionated by electrophoresis using 1.5% agarose gel, and whether the objective
[0086] DNA was amplified was examined.
[0087] The result of the electrophoresis of Nanog gene derived from ES cell was shown in FIG. 1 ; the result of the electrophoresis of Rex1 gene derived from ES cell was shown in FIG. 2 ; and the result of the electrophoresis of CD133 gene derived from ES cell was shown in FIG. 3 , respectively.
(5) Cloning and Nucleotide Sequence Analysis of PCR Amplification Product
[0088] To each 9 μg of 3 kinds of solutions after PCR reaction, which were confirmed amplification by electrophoresis, 1 μL of 10×A-attachment Mix (produced by TOYOBO Co. Ltd.) was added to make the total volume 10 μL, and incubated at 60° C. for 30 minutes to add adenine to 3′-terminal of the PCR amplified products. Next, using QIAquick PCR Purification Kit (QIAGEN, Inc.), low molecular weight DNA was removed according to an attached instruction manual. After that, to the solution after removal procedure of low molecular weight DNA, 1 μL of Ethachinmate (produced by Nippon Gene Co., Ltd.), 5 μL of 3 mol/L sodium acetate (produced by Nippon Gene Co., Ltd.), and 125 μg of ethanol (produced by Wako Pure Chemical Industries Co., Ltd.) were added, respectively, and centrifugal separation was carried out by 18800×g for 10 minutes. Further, the supernatant was removed and washed with 75% ethanol (produced by Wako Pure Chemical Industries Co., Ltd.), and then sterile water was added so as to make the total volume 3 μg.
[0089] To each 3 μL of 3 kinds of solutions which comprise adenine-added PCR amplified products, 1 μL of pGEM-T Easy Vector (produced by Promega Corporation) and 4 μL of DNA Ligation Kit (produced by Takara Bio Inc.) were added to make the total volume 8 μL, and the PCR amplification product was inserted in the vector by incubating this solution at 16° C. for 60 minutes. Next, using QIAquick PCR Purification Kit (QIAGEN, Inc.), purification of the vector was carried out. After that, to the solution after purification treatment, 1 μg of Ethachinmate (produced by Nippon Gene Co., Ltd.), 5 μL of 3 mol/L sodium acetate (produced by Nippon Gene Co., Ltd.), and 125 μL of ethanol (produced by Wako Pure Chemical Industries Co., Ltd.) were added, respectively, and centrifugal separation was carried out by 18800×g for 10 minutes. Further, the supernatant was removed and washed with 75% ethanol (produced by Wako Pure Chemical Industries Co., Ltd.), and then sterile water was added so as to make the total volume 2 μL.
[0090] To each 1 μL of 3 kinds of solutions which comprise the PCR amplified products inserted in a vector, a 40 μL of E. coli (XL10 Gold, produced by Stratagene Corporation, 10 9 cells) was added, and transformation was carried out by the electroporation method. Next, the transformed E. coli cells were cultured in LB agar medium at 37° C. overnight. From colonies of cultured E. coli, a portion was picked up and dissolved in 5.9 μg of sterile water, and to said sterile water, 1 μg of 10×Gene Taq Universal Buffer (produced by Nippon Gene Co., Ltd.), 1 μg of dNTPs mixed solution (each 2.5 mmol) (produced by Nippon Gene Co., Ltd.), 0.1 μg of Gene Taq NT (produced by Nippon Gene Co., Ltd.), and each 1 μg of 2 kinds of 5 μmol/L primers having sequence derived from pGEM-T Easy Vector [5′ CCAGTCACGACGTTGTAAAACG 3′ (Nucleotide sequence 11) and 5′ CACACAGGAAACAGCTATGACC 3′ (Nucleotide sequence 12), designed to give chain length of inserted fragment+250 bp] were added, respectively, to make the total volume 10 μL, and by setting the reactions at 95° C. for 2 minutes, at 95° C. for 20 seconds, at 60° C. for 20 seconds, at 72° C. for 30 seconds as 1 cycle, 30 cycles of colony PCR reaction was carried out. After that, the obtained respective colony
[0091] PCR amplified products were fractionated by electrophoresis using 1.5% agarose gel, and whether the objective DNA was amplified was examined. By employing the colony which was confirmed insertion of the vector, shaking culture was carried out in LB medium at 37° C. overnight. After that, using the cultured broth, plasmid was extracted with the use of QuickGene Plasmid kit SII (produced by Fujifilm Corporation).
[0092] As for the 3 kinds of the obtained plasmids, decoding of nucleotide sequence was carried out by Applied Biosystems 3730×1 DNA Analyzer (Life Technologies Japan Ltd.), with the use of primer having sequence [5′ CACACAGGAAACAGCTATGACC 3′ (Nucleotide sequence 12)] derived from pGEM-T Easy Vector (produced by Promega Corporation).
[0093] The result of decoding of the Nanog gene was shown in FIG. 4 ; the result of decoding of the Rex1 gene was shown in FIG. 5 ; the result of decoding of the CD133 gene was shown in FIG. 6 , respectively.
[0094] In Example 1, using genomic DNA extracted from ES cell, uracilation of non-methylated cytosine in the DNA and amplification of the DNA using the uracilated DNA as a template were attempted according to the method of the present invention. Specifically, non-methylated cytosine in DNA within each promoter region of Nanog gene, Rex1 gene, and CD133 gene which were stem cell marker was uracilated, and amplification of DNA using the DNA after uracilation as a template was carried out. In consequence, from the results of FIG. 1 to FIG. 3 , it turned out that the respective genes in the ES cell were amplified by the method of the present invention.
[0095] Since the DNA after bisulfite reaction would become high thymine content, if high adenine content primer is used, nonspecific amplified products is easy to be formed, it may be difficult to acquire the objective amplification product. Practically, in the Comparative Examples 1 and 2 by the conventional method shown below, sufficient quantity of the PCR amplification product has not been acquired. On the other hand, in the method of the present invention, as is clear from FIG. 1 to FIG. 3 , sufficient quantity of the PCR amplification product has been acquired. Especially, in the PCR amplification of the promoter region of CD133, PCR primer of 60.7% adenine content was used, and although it was PCR amplification in strict conditions, sufficient quantity of the PCR amplification product has been acquired. In the method of the present invention, the reverse transcriptase reaction and the PCR amplification reaction by α-type DNA polymerase were carried out after bisulfite reaction, and it is conceivable that the PCR amplification efficiency was improved as a result of performing these reactions continuously. In particular, since α-type DNA polymerase was used as a DNA polymerase for PCR amplification, it is conceivable that the DNA after bisulfite reaction has been amplified with sufficient accuracy by the proofreading activity. Consequently, from the results of FIG. 1 to FIG. 3 , it turns out that the PCR amplification efficiency by the method of the present invention is good, and the acceptable range is wider.
[0096] In addition, as is clear from the results of FIG. 4 to FIG. 6 , it turned out that any cytosine in Nanog gene, Rex1 gene, and CD133 gene was converted into uracil (on the result of decoding, uracil is written as thymine). Since the cytosine of promoter region of ES cell, which is a stem cell, is not usually methylated, from said result, it was shown that, according to the method of the present invention, all cytosine had been converted into uracil, and cytosine could be converted into uracil with high precision.
Example 2
Uracilation of Non-Methylated Cytosine in the MEF Cell-Derived Nanog Gene, MEF Cell-Derived Rex1 Gene, and MEF Cell-Derived CD133 Gene According to the Method of the Present Invention
[0097] Experiment was carried out by the same way as carried out in Example 1 (1) to (4) except for using MEF cell-derived genomic DNA obtained in Experimental Example 1 as a genomic DNA, instead of using ES cell-derived genomic DNA obtained in Experimental Example 1. That is, using MEF cell-derived genomic DNA, and according to the method described in Example 1, alkaline treatment, bisulfite reaction, reverse transcriptase reaction, and the PCR reaction were carried out, and said amplification product of the PCR was fractionated by electrophoresis using 1.5% agarose gel, and whether the objective DNA was amplified was confirmed.
[0098] The electrophoretic result of Nanog gene was shown in FIG. 1 ; the electrophoretic result of Rex1 gene was shown in FIG. 2 ; and the electrophoretic result of CD133 gene was shown in FIG. 3 , respectively.
[0099] Each amplification product of the above-described PCR reaction which was identified by electrophoresis was subjected to ligation reaction with pGEM-T Easy
[0100] Vector (produced by Promega Corporation) by the same manner as described in Example 1 (5), and after transformation of E. coli , plasmid was collected and the nucleotide sequence was decoded. The decoded result of MEF cell-derived Nanog gene was shown in FIG. 4 , the decoded result of MEF cell-derived Rex1 gene was shown in FIG. 5 , and the decoded result of MEF cell-derived CD133 gene was shown in FIG. 6 , respectively.
[0101] In Example 2, using genomic DNA extracted from MEF cell, uracilation of non-methylated cytosine in DNA and amplification of the DNA using the uracilated DNA as a template were attempted according to the method of the present invention. Specifically, non-methylated cytosine in DNA of each promoter region of Nanog gene, Rex1 gene, and CD133 gene, which were stem cell marker, was uracilated, and amplification of the DNA using the DNA after uracilation as a template was carried out. In consequence, as is the case with the results of using the DNA derived from ES cell in Example 1, it was confirmed that the respective genes in the MEF cell could be amplified by the method of the present invention.
[0102] In addition, as is clear from the results of FIG. 4 to FIG. 6 , it turned out that all the cytosine other than CpG dinucleotide was converted into uracil. It was presumed that the cytosine in CpG dinucleotide, which has not been converted, was methylated one. This is in accordance with many reports that cytosine of the
[0103] CpG dinucleotide in a promoter region is methylated in a differentiated cell such as MEF cell. Therefore, from said result and the above-described result of Example 1 using genomic DNA extracted from ES cell, it turned out that, according to the method of the present invention, only non-methylated cytosine could be converted into uracil with high accuracy.
Comparative Example 1
Uracilation of Non-Methylated Cytosine in the ES Cell-Derived Nanog Gene or ES Cell-Derived Rex1 Gene by Conventional Method
[0104] To each 1 μg of solution containing ES cell-derived Nanog gene or ES cell-derived Rex1 gene, 32.5 μL of sterile water, 5 μL of 10×Gene Taq Universal Buffer (produced by Nippon Gene Co., Ltd.), 5 μL of dNTPs mixed solution (2.5 mmol/each) (produced by Nippon Gene Co., Ltd.), 0.5 μL of Gene Taq NT (produced by Nippon Gene Co., Ltd.), and each 3 μL of 5 μmol/L PCR primer Forward solution and Reverse solution for Nanog gene [Forward: 5′ TTGTGAATTTATAGGGTTGGTGGG 3′ (Nucleotide sequence 5), Reverse: 5′ CAACCAAATCAACCTATCTAAAAACC 3′ (Nucleotide sequence 6)], or each 3 μL of 5 μmol/L PCR primer Forward solution and Reverse solution for Rex1 gene [Forward: 5′ GGGTTATTTGAAGGGTTAGGGGTT 3′ (Nucleotide sequence 7), Reverse: 5′ CTTAAACCCCTCCCTTTTTAAATAA 3′(Nucleotide sequence 8)] were added to make the total volume 50 μL, and by setting the reaction at 95° C. for 2 minutes→at 95° C. for 20 seconds→at 55° C. for 20 seconds→at 72° C. for 30 seconds as 1 cycle, 35 cycles of PCR reaction were carried out. After that, the obtained PCR amplified products were fractionated by electrophoresis using 1.5% agarose gel, and whether the objective DNA was amplified was examined.
[0105] The result of the electrophoresis of Nanog gene was shown in FIG. 1 , and the result of the electrophoresis of Rex1 gene was shown in FIG. 2 , respectively.
[0106] From said result, it turned out that sufficient quantity of the amplification product was not acquired by the conventional method. That is, it turned out that by the conventional method in which the PCR reaction is carried out after bisulfite reaction using a polymerase such as Taq DNA polymerase, sufficient quantity of the amplification product was not acquired.
Comparative Example 2
Uracilation of Non-Methylated Cytosine in the MEF Cell-Derived Nanog Gene or MEF Cell-Derived Rex1 Gene by Conventional Method
[0107] The PCR reaction was carried out by the same way as carried out in Comparative Example 1 except for using a solution containing MEF cell-derived Nanog gene and MEF cell-derived Rex1 gene, which were obtained by the bisulfite reaction in Example 2 (2), instead of using a solution containing ES cell-derived Nanog gene and ES cell-derived Rex1 gene. After that, the obtained PCR amplified products were fractionated by electrophoresis using 1.5% agarose gel, and whether the objective DNA was amplified was examined.
[0108] The result of electrophoresis of Nanog gene was shown in FIG. 1 , and the electrophoresis result of Rex1 gene was shown in FIG. 2 , respectively.
[0109] From said result, it turned out that sufficient amount of amplification product has not been obtained by the conventional method. That is, even if it was a case where MEF cell-derived DNA was used, it turned out that, just as Comparative Example 1, sufficient amount of amplification product was not obtained by the conventional method. | The invention provides a method for obtaining DNA after bisulfite reaction which can be stored with libraries in genome reserved and has excellent storage stability, and a method for detecting methylated cytosine. Specifically, the invention provides a method for obtaining DNA complementary to single-stranded DNA in which non-methylated cytosine has been uracilated by subjecting single-stranded DNA to a bisulfite reaction and then a reverse transcriptase reaction. The resulting complementary DNA can be amplified by a PCR reaction. Methylated cytosine can be detected in single-stranded DNA by subjecting the single-stranded DNA, in order, to a bisulfite reaction, a reverse transcriptase reaction, and a PCR reaction, and then subjecting the obtained PCR amplification product to nucleotide sequence analysis. | 2 |
FIELD OF THE INVENTION
The present invention relates to a safety cap which is used to close a container containing steam under pressure, such as, for example, the boiler of a steam generator.
BACKGROUND OF THE INVENTION
European Patent No. 0 337 528 discloses a safety cap for a container containing steam under pressure, comprising a closure member screwed onto the mouth of the container, an external knob which the user can turn to screw the closure member on and off, and an internal diaphragm which is moved by the action of the pressure of the steam. When the pressure of steam in the container is zero or low, the diaphragm is in a rest position, and the closure member and knob are coupled in rotation to allow the cap to be unscrewed. As the pressure of the steam rises, the diaphragm moves into an operating position and uncouples the knob from the closure member to prevent the closure member from being unscrewed.
This safety cap therefore prevents the container from being opened when there is high steam pressure inside it and prevents the pressurized steam from escaping violently and injuring the user.
This safety cap finds advantageous application in, for example, the boilers of steam generators for domestic use, e.g. for supplying steam irons, cleaning equipment, etc. Its virtue is that the domestic user is often technically unskilled and therefore lacks the necessary awareness and understanding to handle a pressure boiler.
It is precisely because of the great danger represented by a container of steam under pressure, and the inexperience of those who usually use it, that it is so important to improve the closure cap of the container in such a way as to lower the risk margin, and hence the likelihood of accidents, towards zero.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a safety cap that satisfies this requirement.
This object is achieved by means of a safety cap of the type described above, characterized in that it comprises a manometer, incorporated in the cap and readable from the outside, which detects the pressure of steam in the container.
BRIEF DESCRIPTION OF THE DRAWINGS
The invention will be understood more clearly from the following description of a non-restrictive example of an embodiment thereof, illustrated in the accompanying drawings in which:
FIG. 1 is an exploded perspective view of a safety cap according to the invention;
FIG. 2 shows two components of the cap of FIG. 1 in a different exploded perspective view;
FIGS. 3, 4 are two views in longitudinal section showing how the cap of FIG. 1 works;
FIG. 5 shows in plan view how a mechanism of the cap of FIG. 1 works; and
FIG. 6 is a perspective view of the cap of FIG. 1 in the assembled state.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
The cap illustrated, which is given the general reference 10, comprises a closure member 11 and a knob 12 connected to it.
The closure member 11 is internally hollow and comprises a cylindrical head 13 and an internally threaded shank 14, also cylindrical. The head 13 includes an external toothed ring 15 which fits into an internal annular throat 49 in the knob 12. On the top of the head 13 there is also a spider part 16. Inside the head 13, a cavity 17 is bounded at the bottom by an arcuate wall 18 containing an eccentric hole 19 allowing communication between the cavity and the interior of the shank 14. The cavity 17 houses an elastic diaphragm 20 which is securely attached all the way around its circumference to the walls of the cavity. The bottom end of a bush 21 rests on the diaphragm 20. Resting on the top end of the bush 21 is a disc 22 with four longitudinal teeth 23 and four radial teeth 24 around its perimeter; the longitudinal teeth 23 fit into the spaces between the arms 16' of the spider 16, while the radial teeth 24 fit into the spaces between four internal projections 25 from the knob 12.
A manometer 26 is incorporated in the knob 12. The manometer 26 comprises a base 27 which includes a downward stem 28 that passes through an axial through hole 29 in the disc 22 and into the inside 30 of the bush 21. The base 27 supports a flat, elliptically-sectioned tubular component 31 extending in an arc of a circle. One end of the tubular component 31 is connected to one end of a tube 32 of small section. The tube 32 runs down through the stem 28, passes out of the stem and then out of the bush 21 through a longitudinal slot 33 in the bush itself and enters through a transverse through hole 34 in the head 13 of the closure member 11. This hole 34 opens into the space between the wall 18 and the diaphragm 20 so that the tube 32 places this space in communication with the inside of the tubular component 31. At the opposite end from that connected to the tube 32, the tubular component 31 is connected to a rod 35 which in turn is hinged to a lever 36 integral with a sector gear 37; the sector gear 37 meshes with a pinion 38 attached to an indicator needle 39. The indicator needle 39 is mounted on a dial 40 showing a graduated scale 41 giving pressure values. The manometer 26, which weighs very little, is supported simply by resting on a horizontal length of tube 32 on the head 13 of the closure member 11 and is fixed in position by a plate 42 attached to the tube 32 and inserted in a seat 43 formed in the spider 16. The indicator needle 39 and the dial 40 lie behind a transparent wall 44 in the top of the knob 12.
The cap 10 as described and illustrated is intended to close a container in which steam is generated under pressure, e.g. the boiler of a steam generator designed for use in the home. This container of which FIGS. 3 and 4 show a portion of the upper wall, marked A, in section, includes an externally threaded mouth B allowing communication between the interior of the container and the outside. The cap 10 is fitted to the container by screwing the threaded shank 14 of the closure member 11 of the cap onto the mouth B. To screw the cap 10 on, the user rotates the knob 12, which transmits rotary motion to the toothed disc 22 because of the engagement of the projections 25 of the knob with the teeth 24 of the disc, and the disc 22 in turn transmits rotary motion to the closure member 11 because of the engagement of the teeth 23 with the arms 16' of the spider 16. A seal 45 is housed in the root of the shank 14 and projects radially inwards from the root to provide leaktightness between the closure member 11 and the mouth B.
Operationally, with reference to FIGS. 3 and 4, when pressurized steam is generated in the container, this pressurized steam passes into the cap 10 as far as the cavity 17 upstream of the diaphragm 20 via the hole 19, and acts on one side of the diaphragm pushing it upwards as shown in FIG. 4. The upward movement of the diaphragm 20 causes an upward movement of the bush 21 and hence of the disc 22, so that the teeth 23 of the disc 22 disengage from the arms 16' of the spider 16 and the teeth 24 of the disc disengage from the projections 25 of the knob 12, the result of which is that there is no longer any connection between the closure member 11 and the knob 12. At the same time the steam enters the tube 32 through the hole 34 and reaches the hollow tubular component 31; the pressure of the steam causes the curvature of this part 31 to change and, as shown in FIG. 5, by means of the rod 35, lever 36, sector gear 37 and pinion 38, the needle 39 is caused to rotate to a point on the graduated scale 41 corresponding to the value of the pressure in the container.
In this way the operator, by simple observation of the manometer 26, and in particular the position of the needle 39, through the transparent wall 44, is made aware of the existence of pressurized steam inside the container. If, nonetheless, the operator tries to unscrew the cap 10 by turning the knob 12 in spite of the indication provided by the manometer 26, the knob will rotate loosely round the closure member 11 since it has been disconnected from the latter, thus preventing the unscrewing of the cap. In its loose rotation about the closure member 11, the knob 12 is guided by the connection between the ring 15 and the throat 49.
A transverse through hole 46 is formed in the shank 14 of the closure member 11 at an intermediate point along its length. If for any reason the user does manage to unscrew the cap 10 while there is still steam under pressure inside the container, the hole 46 will open onto the exterior before the cap is fully unscrewed and the steam under pressure will thus vent to the outside through this hole, thus warning the operator of the presence of steam under pressure in the container.
When the pressure of steam in the container drops or reaches zero, the diaphragm 20 sinks back down to its initial position as shown in FIG. 3. The bush 21 sinks with the diaphragm 20 so that the teeth 23 of the disc 22 re-engage with the arms 16' of the spider 16 and the teeth 24 of the disc re-engage with the projections 25 of the knob 12, reconnecting the knob to the closure member and thereby making it possible to unscrew the cap from the container. Should the abovementioned components not engage immediately with each other, the initial rotation of the knob 12 will be sufficient to bring such engagement about.
It will be clear from the aforegoing that the cap 10 offers valuable safety guarantees, avoiding the risk of accidents due to sudden escapes of pressurized steam from the container or, in the most serious case, explosion of the container due to excessive pressure. In particular, the combination of the manometer with the system for mechanically uncoupling the closure member from the knob gives enhanced security since the operator is first given a visual indication of the dangerous situation and, if that goes unnoticed, the operator is still protected by the mechanical uncoupling. Obviously the vent hole 46 represents yet another safety feature.
The location of the needle 39 and of the scale 41 at the top of the cap allows them to be read immediately.
The graduated scale 40 is preferably divided into two bands, namely a green-colored band corresponding to zero pressure or low pressures in the container, followed by a red-colored band corresponding to higher pressures in the container at values at which the container must not be opened.
It may be remarked that the high degree of safety is provided with a cap having the same dimensions as known caps of this type thanks to the compact dimensions of the manometer 26 components. The path followed by the tube 32 of the manometer 26 for collecting the pressure signal from upstream of the diaphragm 20 is particularly advantageous inasmuch as it does not obstruct the correct working of the mechanical uncoupling system; the slot 33 in the bush 21 allows the bush to move relative to the tube 32 during the movement of mutual mechanical coupling or uncoupling of the closure member 11 and knob 12.
The eccentric position of the hole 19 and the radially inward-projecting position of the seal 45 that comes partly over the hole, protect the hole from spurts of boiling water and thus prevent lime from forming in the hole and blocking it up.
The knob 12 comprises a cylindrical skirt 47 in which the internal components of the cap 10 are enclosed and which extends past the lower end of the shank 14 of the closure member 11; the knob also comprises an internal transverse annular closing wall 48 through which the shank 14 passes. The skirt 47 protects the internal components of the cap 10 and its lower end part 47' prevents anyone from getting access to the shank 14 with a tool and trying to turn the closure member 11 when the container is holding pressurized steam and the closure member 11 and knob 12 are uncoupled from each other; the wall 48 protects the underside of the internal components of the cap and prevents access to these.
Variations and/or additions to what has been described above and illustrated are obviously possible.
The configuration both of the parts that make up the cap and of their details may vary; for instance, variations of the shape of the components and/or variations in the number of their details (arms, teeth, projections) may be envisaged.
The manometer here described and illustrated proves, as seen earlier, to be particularly advantageous. However, the use of other types of manometer must not be ruled out.
The cap here described and illustrated may obviously be applied to any container under pressure to satisfy the requirements of a high degree of safety. | A safety cap for containers under steam pressure contains internally a diaphragm that is actuated by the pressure of steam in such a way as to break the mechanical connection between a closure member forming part of the cap and screwed onto the container, and a knob forming part of the cap and by means of which the latter can be screwed on and off. In order to increase the safety features of the cap, the latter is fitted with a manometer, incorporated in the cap and readable from the outside, which detects the pressure of steam in the container. | 5 |
BACKGROUND OF THE INVENTION
This invention relates to railroad track working equipment and is particularly concerned with a machine for driving spikes in ties.
In railroad track construction, the rails are laid on tieplates which rest between the tie and the rail. The tieplates are then fastened to the ties by spikes. Generally, two spikes are used for each tieplate, one on each side of the rail. Holes are provided in the tieplate to receive the spikes.
Driving the spikes requires that they be properly aligned with the holes in the tieplate before the driving pressure is applied. This is done with the use of spike holders. Once the spike is aligned, the driver must hit the spike precisely on the head or it will be bent out of shape or improperly driven.
To achieve a high rate of production, the number of misdirected drive strokes must be kept to a minimum. This requires precise alignment of the spike driving mechanism. Early versions of high production spike driving machines used a high impact, hammer-like drive stroke. Because of the high speed of this drive stroke, it was impossible to align after the stroke had been initiated so the only alignment took place while the mechanism was in its fully raised position. This resulted in a high number of miss-hits due to the difficulty of aligning the driver. Later machines used a slower drive stroke. This provided some opportunity for correction of the driver position but still did not permit precise location just before the driver came in contact with the spike.
SUMMARY OF THE INVENTION
An object of this invention is to provide precise control over the alignment of a railroad spike driving mechanism with the spike to be driven.
Another object is the proportional control of the horizontal position of the spike driver.
Another object is the proportional control of the vertical speed of the spike driving mechanism.
Another object is the control over when the spike driving mechanism will move upwardly from its driving position.
Another object is the capability of maintaining the driver in a dwell position at any point in its drive or return strokes.
Another object is a control system for a railroad spike driving mechanism which can be operated in one hand so that a single user can drive two spikes in a tieplate at the same time.
Other objects will appear from time to time in the ensuing specification and drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side view of a portion of the spike driving machine, showing the parts necessary for locating the driver.
FIG. 2 is a section on an enlarged scale taken along line 2--2 of FIG. 1 with parts omitted;
FIG. 3 is a schematic of the control circuit for the spike driver vertical position; and
FIG. 4 is a schematic of the horizontal control system.
DESCRIPTION OF THE PREFERRED EMBODIMENT
FIGS. 1 and 2 show the parts of a spike driving machine which are involved with the control system of the present invention. Portions not directly involved with locating the spike driver, such as the engine, hydraulic pump and spike storage bins, have been omitted. The machine has been shown as including a frame 10 with an axle 12 at each end and flanged wheels 14 at the end of each axle adapted to engage a conventional rail 16 of railroad track with the rails on tieplates 18 which in turn rest on the ties 20, all of which is conventional. The machine may be driven by a suitable engine (not shown) mounted on the frame in any desired manner. The engine drives a pump or hydraulic circuit which in turn operates the various parts of the unit and may also propel the machine along the track. The various parts that go to make up the frame will not be described in detail, it being understood that the frame may be made of suitable angle irons, channels, braces, beams and the like, all suitably connected together, such as by welding or the like, into a desirable rigid and sturdy structure to support the various parts and to provide suitable openings for the various operative parts. The frame supports a spike driving assembly, indicated generally at 22 in FIG. 1, rail clamp assemblies at each end as at 24 and a set-off mechanism indicated at 26. The frame may also support seats 28 for the operator. The various hydraulic controls are shown in FIGS. 1 and 2 near the operator's seat as will be explained in detail in connection with the control circuit.
The carriage and spike driving assembly 22 shown in FIGS. 1 and 2, may include four vertical posts 30 disposed in a square or rectangle, on one side of the frame laterally so that it is disposed over one of the rails. Each post may take the form of a tube or cylinder with a stub shaft or dowel 32 pinned and projecting above the upper end. A frame mechanism is slidably mounted on the pins or dowels 32 and includes longitudinal beams 34 having holes or sleeves toward each end which fit down over the pins or dowels 32 and are constructed to abut the top of the tubes or posts 30. The ends of the beams 34 are connected by shafts 36, one at each end which, together with the beams, make up a box-type frame. This box-type frame is adapted to be raised or lowered on the pins 32 by two piston and cylinder assemblies 38, one on each side.
The shafts 36 support a movable carriage 40 which is constructed to be moved laterally or at right angles to the rails so as to position the spike driving cylinders or "guns" in a manner explained later. The carriage 40 includes sleeves 42 shown as three on each shaft 36 in FIG. 2, which are interconnected by spacer bars 44 which may be welded to them. Also, each shaft 36 carries a beam 46 swung beneath it by the sleeves 42 and the beams are joined to each other by slide rods 48, shown in this case as four. The slide rods 48, beams 46, spacer bars 44 and the sleeves 42 make up the carriage which, as a unit, is adapted to slide in either direction across the rails.
A sub-carriage 50 is mounted on the slide rods 48 and is adapted to slide either forward or backward in a direction generally parallel to the rails. The sub-carriage may be divided into a left and right hand side 50A and 50B, each of which is in the form of a box-type frame with suitable openings to slide on the rods 48. A hydraulic cylinder 52 may be mounted as at 54 on the end of one of the beams 34 of the main frame with its piston rod connected to one of the sleeves 42 of the carriage 40. Since the cylinder 52 is disposed laterally, it will move the main carriage in a direction across the rails.
Two cylinders 56 are pivoted as at 58 to one of the spacer bars 44 with their piston rods connected at their other end to a suitable upstanding bracket 60 on the box-type sub-frame 50 so that the operation of these cylinders will move the sub-frame longitudinally parallel to the rails. The lower surface of each sub-frame may support a depending spike driving piston and cylinder which is commonly referred to as the spike driving gun indicated at 62 with its upper end adjustably mounted on the bottom of the sub-frame. One of the guns drives spikes outside the rail and the other inside.
The main upper frame comprising beams 34 and shafts 36 may be raised and lowered on the dowels or pins 32 by the cylinders 38. For travelling, the pistons 38 raise the upper frame which raises the carriages, sub-carriages and spike driving guns a suitable distance so that a lock tube 64, C-shaped in cross-section, may be slipped around the exposed upper portion of the piston rod and left in a place so that when a lift cylinder 38 is released, the weight of the upper frame, carriages and driving guns will be taken by the lock tube.
Each of the spike driving guns 62 has a lower frame 66 (FIG. 1) attached to it which may include a pair of pivoted spike holding jaws and a spike feed shute 68. The shute supplies spikes, one at a time, to a position under the piston or driver 70 of the spike gun to be driven through the hole in the tie plate into the tie.
It will be understood that the structure described to this point is conventional and is generally the same as that shown in U.S. Pat. No. 3,717,101, issued Feb. 20, 1973 and assigned to this assignee.
This invention is concerned with controlling the above-described mechanism in such a manner as to provide precise alignment of the spike driving gun with the spike. This is accomplished by allowing horizontal alignment of the gun as it proceeds downwardly. This means the operator can make last second adjustments as he sees exactly where the driving guns are coming down. This simultaneous control of both the gun's vertical position and horizontal position is provided in the following manner.
A control arm 72, as shown in FIG. 1, is suspended before the operator, attached to the sub-carriage 50 by bracket 71 and vertical support 73. Resistance strain gauges 74 are mounted on the arm 72. As shown in the diagram of FIG. 4, the strain gauges are electrically connected by leads 75 to an appropriate bridge circuit located in a box 76. When the operator pushes or pulls on the control arm, the strain gauges create an imbalance in the circuit thereby inducing a proportional carriage control signal. This signal is fed to a proportional control valve 78 which operates carriage cylinders 52 and 56 via three-way valves 80 and hydraulic lines 82. Thus, minute adjustments can be made in the horizontal position of the spike driving mechanism.
Strain gauges can be mounted on the control arm such that longitudinal and lateral control of the carriage is possible. In general, however, it is only necessary to provide fine adjustment of the longitudinal carriage position. This is so because once the machine has been set up, a reference line is established which sets the lateral position of the carriage. This is explained in detail in the above referred-to U.S. Pat. No. 3,717,101.
Although a single control arm is shown in FIG. 2, dual control arms could be provided to permit independent control of the spike driving guns 62. This would necessitate the removal of a strap 84 (FIG. 2) from the sub-carriages 50A and 50B so that they move independently on the slide rods 48.
The spike driving gun control is shown schemmatically in FIG. 3. This control includes a handle or grip 86 attached at the bottom of the control arm 72. The handle has a shroud or trigger switch 88 which is spring-biased as at 90 to normally cover a plurality of light emitting diodes 92. When uncovered, these light emitting diodes or LED's generate signals which are connected in parallel through resistors 94 to the input of an operational amplifier 96. This amplifier has a resistance feed back loop 98 causing it to act as an adder of the incoming signals in the known manner. As the operator squeezes the trigger switch 88, the LED's become uncovered one at a time, and the signals are then added by the amplifier circuit. In theory, this would provide a stepwise increasing output from the amplifier but it has been found in practice to provide a gradually increasing output. This output is then connected to an OR gate 100 and from there to a proportional control valve 102. Energization of the operational amplifier sets three-way control valve 104 in a down mode such that fluid pressure is applied to the top of the spike driving gun 62 thereby causing the piston and rod 70 to move downwardly. The level of the signal provided to the proportional control valve, governs the pressure fed to the cylinder so that the speed of the downward motion is controlled thereby, which means the operator can control the speed of the spike driving gun by the number of LED's he has uncovered with the trigger switch. For example, when starting a drive stroke from a fully raised position, the operator can squeeze the trigger to energize all of the LED's and provide the fastest downward motion. As the rod approaches the spike head, the operator can allow the shroud to gradually cover the LED's again, slowing the downward stroke so that the last second horizontal adjustments of the gun position can be made by deflecting the control arm as explained above.
The initiation of a return stroke is governed by the existence of signals from LED's 106 and 108. The first of these is mounted on the grip 86 and is normally covered by an auxiliary shroud 110. When the trigger switch 88 is squeezed, it will also cover the LED 106 blocking out any possibility of a raise signal being generated during a down stroke. The secondary LED 108 is positioned such that a vane 112 on the piston and rod assembly will cover the LED when the piston is in its fully raised position. Thus, as the piston returns from a drive stroke, the return stroke will conclude as the vane cover the LED 108.
LED's 106 and 108 are connected to an AND gate 114 whose output is then fed to OR gate 100. Therefore, both LED's must be uncovered before a return stroke can be initiated. When both the trigger switch 88 and auxiliary shroud 110 are in a normal position, neither a drive stroke nor a return stroke can take place. In this condition, the three-way valve 104 assumes a neutral mode and the spike driving gun will dwell at whatever position it has last attained. To raise the spike driver, the operator must release the trigger switch 88 and rotate the auxiliary shroud 110 and, of course, the piston and rod assembly must be in a lowered position so LED 108 is not covered by vane 112.
It can be seen then that the operator can control the vertical and horizontal position of the spike driving gun by manipulating controls maintained in one hand. While the preferred form and alternate arrangements have been shown and suggested, it should be understood that suitable additional modifications and alterations may be made without departing from the invention's fundamental theme. | In a railroad spike driving machine, the spike driving mechanism is centered over a spike by a system which provides simultaneous proportional control over both the vertical and horizontal positions of the spike driver. The driver is mounted on a carriage whose position is adjustable according to signals derived from the deflection of a control arm. Strain gauges mounted on the control arm sense the push or pull of the operator to adjust the carriage position. The speed of the drive stroke of the hydraulic spike driver is governed by a proportional control valve which is in turn controlled by a signal generated from a trigger switch on the control arm. | 4 |
CROSS-REFERENCE TO PRIOR RELATED APPLICATION
This application is a continuation-in-part of application Ser. No. 08/390,103 filed on Feb. 17, 1995, now U.S. Pat. No. 5,575,020.
FIELD OF THE INVENTION
The present invention relates to plumbing fixtures and more particularly relates to a urinal which is adapted for use by both men and women and which urinal provides convenience and significant water savings.
BACKGROUND OF THE INVENTION
The conventional toilet discharges approximately between 1.6 and 5 gallons of water into the toilet bowl and sewer when it is flushed. Recently, consistent with the recognition of a need for water conservation, toilets have been designed which utilize less volume of water by incorporating water saving devices such as valves which achieve negative buoyancy so that the valve is closed prior to discharge of the entire contents of the toilet tank. However, even with such low water consumption devices, the normal flushing operation will discharge over one gallon of water per flush into the sewer. While this quantity of water may be necessary for flushing some materials such as fecal matter and paper, this quantity of water is in excess of the amount normally required for proper flushing of urine.
Apart from the problem of water conservation, conventional toilet design does not provide the convenience and expediency of a urinal. It is not uncommon, particularly at public facilities, for long lines to form at rest rooms. This is particularly true at women's rest rooms because women's rest rooms do not provide convenient urinals of the type found in men's rest rooms. Accordingly, there exists a need for an improved urinal which provides convenience of use.
THE PRIOR ART
The prior art discloses a number of urinal attachments for toilet bowls. For example, U.S. Pat. No. 3,412,408 discloses a bowl-like urinal adjustably positionable and attachable to a toilet. The device has a flexible, disposable drain duct which discharges into the toilet bowl. While the device shown in this patent is convenient for use by men, it is not generally suitable for use by women and does not result in water savings since the contents are discharged into the toilet bowl requiring a full cycle flushing operation.
U.S. Pat. No. 4,145,768 discloses a water conserving urinal having an open top funnel which can be mounted on a wall adjacent the toilet with a flexible hose extending from the funnel to the U-shaped gas trap section of an adjacent sink or water basin.
U.S. Pat. No. 4,282,611 discloses a urinal adapted for attachment to a toilet bowl which has a bracket arm connected to the toilet seat anchor bolts and which device extends laterally of the toilet bowl. A swing arm is pivotally connected to the bracket arm and supports a funnel. In the use-position, the funnel and stem are in registry with the toilet bowl and in the non-use position they are pivoted or swung out of registry with the toilet bowl. Again, while the device provides the convenience of a urinal, it does not result in water savings and the device also has certain sanitary concerns in that in the non-use position, urine not drained from the device could easily drip onto the floor, wall or toilet.
U.S. Pat. No. 4,985,940 shows a plumbing fixture for installation in women's rest rooms. An elongate, flexible hose has a funnel at its top and communicates with a water-holding bowl that is flushed by a siphoning action. A sanitary cuff extends around the rim of the funnel so that the funnel does not contact the user. The cup is removed from the funnel after use by an ejector arm when the funnel is placed between the arms of a hanger member.
U.S. Pat. No. 5,153,947 shows a urinal attachment for a floor-mounted toilet. The urinal has a bowl adjacent the toilet and an outlet in the bowl connects to a drain line fitting which attaches to the toilet base. The drain line of the urinal bowl is connected to a drain fitting so that it bypasses the toilet bowl and yet is periodically rinsed by a water line. Use of this device could result in noxious odors from the drain pipe being communicated to the rest room by means of the device.
U.S. Pat. No. 4,683,598 shows a urinal adapted for use by females which has a flexible tube with a flared upper end shaped to conveniently fit the female anatomy and collect urine which drains down through a flexible line to a collection bowl. The collection bowl may be located on a floor or against a wall.
U.S. Pat. No. 4,137,579 discloses a plumbing fixture having a receptacle with a tube forming a P-trap at its lower end. The P-trap is coupled to a standard toilet by an expandable grommet. The receptacle has a hollow handle which serves as a water distribution control means to supply water to a tubular hollow rim of the receptacle. An eye is provided as part of the receptacle to enable the device to be hung in a storage position between uses.
Co-pending patent application, now U.S. Pat. No. 5,390,374, discloses an improved water-conserving urinal for both males and females which is attachable to the toilet. The urinal bowl is supported on a flexible member secured at its lower end to a pivot member. Water is supplied to the bowl from the toilet water supply line via flexible supply line. A flush valve is provided in the water line and distributes a low volume of water around the bowl by means of an interiorly located flush ring. A waste line extends from the discharge of the urinal bowl to the sewer. Fluid waste is discharged directly to the sewer line without the necessity of a full flush of the toilet resulting in substantial water savings. The pivoted flexible support permits the urinal to be moved forward to the desired position and height to accommodate the requirements of the user.
Therefore, while the above devices and others which may be found in the prior art due to some extent provide convenience of a urinal and also provide water saving features, there nevertheless exists a need for an improved urinal which will result in water savings and which is adaptable for use by both men and women and which device is both functionally and aesthetically acceptable.
SUMMARY OF THE INVENTION
Accordingly, it is a broad object of the present invention to provide a water conserving urinal assembly which is convenient and is adapted for use by both men and women.
It is another object of the present invention to provide a urinal which may be conveniently mounted to existing toilet bowls or attached to existing plumbing fixtures.
Another object of the present invention is to provide a urinal which may be used in either private residential or public rest rooms.
It is another object of the present invention to provide a urinal which results in substantial savings of water.
Another object of the present invention is to provide a urinal which is mounted to a toilet bowl or to an area adjacent the toilet to provide convenience of use and which permits the device to be stored in a convenient, out-of-the-way position.
Another object of the present invention is to provide a urinal which may be plumbed to a conventional toilet or other waste line and which discharges directly into the sewer.
Another object of the present invention is to provide a urinal having a protective cover to which the urinal may be attached in a stored position.
SUMMARY OF THE INVENTION
Briefly, in accordance with a preferred embodiment of the present invention, a urinal is provided which includes a urinal bowl which is attached to a flexible waste line. The waste line may be connected to a sewer line through a fitting at the base or pedestal of the toilet or may be directly attached to a drain line of a plumbing fixture such as a wash basin. A flexible waste line may also be extended through the toilet bowl into the waste or sewer line to drain directly into the sewer line when flushed without the necessity of flushing the toilet and without special plumbing requirements.
The urinal bowl is detachably securable at a hanger which may be attached to the toilet tank or attached at a convenient location such as to the wall adjacent the toilet. The hanger has receiving channels which will engage the bowl in the stored position and which permit the bowl to be disengaged from the hanger when used. The hanger also provides a cover over the bowl in the stored position and includes a flush ring which is attached to a source of flush water. A flush valve is operated to discharge water into the attached bowl when necessary. Preferably, the flush valve is actuated by a button located on the cover. The source of water may be the toilet tank, in which case the flush water line depends into the toilet tank and into a filter reservoir. The source of flush water may also be an existing water line such as the filler line supplying the flush tank in which case it is necessary to provide a connection into the water line.
In the preferred embodiment, the urinal bowl has a narrow front edge and diverges rearwardly having a general triangular or keyhole shape. This configuration facilitates convenient use both by men and women.
In another embodiment, the urinal bowl has an integral cover which is pivotally attached to the bowl and is spring biased to a closed position. Moving the cover to an open position and allowing it to return to a closed position will actuate a flush valve directing water into the bowl.
BRIEF DESCRIPTION OF THE DRAWINGS
The above and other objects and advantages of the present invention will become more apparent from the following description, claims and drawings in which:
FIG. 1 is a perspective view showing a preferred form of the urinal of the present invention attached to a conventional toilet with the urinal shown in a stored position;
FIG. 2 is a view similar to FIG. 1 with the urinal shown removed from its stored position;
FIG. 3 is a front view of the urinal bowl and cover;
FIG. 4 is a front view of a toilet with the urinal attached and with a part of the tank broken away to illustrate use of the toilet tank reservoir as the flush water supply for the urinal and a part of the hanger broken away to illustrate the flush ring;
FIG. 5 is a front view of a toilet showing the urinal bowl attached to a wall adjacent the toilet and with the bowl connected to the water filler line;
FIG. 6 is a perspective view of yet another embodiment of a urinal according to the present invention;
FIG. 7 is a sectional view taken along line 7--7 of FIG. 6;
FIG. 8 is a sectional view of the urinal bowl shown in FIG. 6 in a closed position with the open position shown in dotted;
FIG. 9 is an exploded view of the urinal of FIG. 8;
FIG. 10 is a front view of a urinal of the type shown in FIGS. 8 and 9, wall mounted and adjacent a toilet and plumbed to the waste line and water supply of an adjacent wash basin;
FIG. 11 is a front view of yet another embodiment of the invention shown wall-mounted adjacent a sink and waste line;
FIG. 12 is a cross-sectional view taken along line 12--12 of the urinal shown in FIG. 11;
FIG. 12A shows an alternate valve for use with the embodiment of FIG. 11 when connected to a water supply;
FIG. 13 is a perspective view of the urinal shown in FIG. 12;
FIG. 13A is a detail cross-sectional view of an alternate fill valve;
FIG. 14 is a perspective view of a urinal of the type shown in FIG. 12A;
FIG. 15 is a cross-sectional view of another embodiment of the urinal of the present invention; and
FIG. 15A is a detail cross-sectional view of the pump chamber shown in FIG. 15;
FIGS. 16, and 17 are cross-sectional views of a waste line connector for attachment in a conventional waste water or drain line as seen connected to the waste line in FIG. 11.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Turning to the drawings, FIGS. 1 to 4 show a preferred form of the present invention which is generally designated by the numeral 10 and is shown in conjunction with a conventional toilet which has a toilet bowl 12 and a tank 14 with a cover 11. The tank is supplied with water by means of a water line 16 and filler line 18. A conventional shut-off valve 20 is provided in the water line 16. The water in tank 14 may be selectively discharged into the toilet bowl by operation of a trip handle 15 which will lift the ball or other valve member from the valve seat within the bottom of the tank allowing the water to be discharged into the toilet bowl and across the trap section 22 of the toilet into the sewer line 26. The toilet is secured to the floor by a plurality of hold down nuts 28 secured to bolts which extend through the flange 29 at the base of the toilet. As is conventional, the tank and the toilet bowl and are ceramic and the lid assembly 30 is secured to the toilet bowl by bolts at the rear of the seat assembly. The construction described above is conventional and is set forth to facilitate an understanding of the present invention as the present invention may be attached and used with conventional toilets of the type described.
The urinal device 10 includes a bowl 50, as best seen in FIG. 2, which is preferably molded from a suitable rigid and chemically-resistant plastic such as PVC, ABS or the like. The bowl has a side wall 52 which terminates at an upper rim 54 having a bead or lip 55 extending at least partially around the rim. The bowl may be configured in various shapes but preferably is generally pyriform as shown having narrow front 56 which diverges into a larger rear section 58.
The bowl downwardly converges to a funnel portion 60 which terminates at a lower outlet 62. The lower end of the funnel is preferably formed as a cylindrical member 64 to provide a convenient surface for gripping by the user. One end of flexible waste line 70 communicates with the sewer line 26 at quick connect fitting 72. Quick connect fitting 72 is located in the base of the toilet communicating with the sewer line below the level of the water seal in the trap. Quick connect fitting 72 allows the flexible line 70 to be easily and quickly disconnected from the toilet, if required, for repair. The quick connect fitting can be either provided as a OEM component of the toilet or may be retrofit by drilling a hole through the base of the toilet at the appropriate location aligned with the sewer.
As seen in FIGS. 1 and 2, the bowl 50 is received or "parked" in a hanger 80 in the stored position. The hanger 80 has a downwardly curved top wall 82, a front wall 84, a rear wall 85 and a side wall 86. The hanger is suspended from the side wall of the toilet tank by a generally U-shaped hook 88. The rear wall 85 and the front wall 84 are provided with oppositely positioned, rearwardly extending flanges or channels 90 and 92. The flanges turn inwardly so as to engage the bead or lip 55 on the rear portion of the bowl. In this way, the bowl can be engaged in the hanger in the stored position as shown in FIG. 1 by aligning the upper rim of the bowl with the flanges 90, 92 and manually moving the bowl rearwardly until the bowl is in abutment against the rear wall 85 in the fully engaged and stored position. As indicated, area 64 is provided for convenient gripping of the bowl for removing the bowl and for returning it to the stored position. With the urinal bowl in the stored position, the hanger 80 serves as a cover over the urinal bowl for aesthetic, sanitary and functional reasons.
As best seen in FIG. 4, the hanger houses a flush ring 100 which flush ring is shaped to conform to the shape of the interior of the bowl. The flush ring is mounted within hanger 80 at a location above the rim of the bowl when the bowl is in the housed or stored position seen in FIG. 2. The flush ring is preferably molded of plastic tubing and has a plurality of spaced-apart nozzles 102 which serve to direct water downwardly and inwardly along the interior walls of the bowl. The flush ring may be fabricated as an integral part of the cover or may be separately fabricated and secured to the cover interior by appropriate fasteners.
Water supply line 110 connects to the flush ring across flush valve 112. Valve 112 is opened by depressing valve actuator button 114 which is centrally located on the cover 82. Depressing button 114 will allow water to flow into the flush ring and be discharged into the subjacent bowl 50 to flush and rinse the bowl.
Water supply line 110 is connected to the flush ring and is a flexible hose which extends between the tank cover 11 and the toilet tank 14 and depends into the toilet bowl as seen in FIG. 4. Hook 88 from which hanger 80 is suspended will space the tank cover 11 from the upper edge of the tank 14 a sufficient distance to provide clearance through which the water line 110 may extend. The inlet end of the line 110 terminates at a location above the floor of the tank depending into reservoir 120. Reservoir 120 is cup-shaped and may be molded plastic and is attached to the interior tank wall or may be attached to the end of the water inlet line 110. A filtering material 122 such as cellular foam may be placed within the reservoir.
When installed, the bowl is in the normal stored or "parked" position as shown in FIG. 1 which places it out of the way and positions the urinal bowl convenient for use. In this position, the urinal bowl is covered by the hanger 80 making it aesthetically acceptable and also sanitary. When it is desired to use the device, the user will grasp the urinal bowl about the handle 64 and pull the bowl forward so that it disengages from the hanger 80. The user then positions the urinal bowl at the desired use location which is accomplished due to the flexibility of waste line 60.
After use, the user will reinsert the urinal bowl into the hanger by engaging the bowl rim 55 with the flanges 90 and 92 and moving the bowl rearwardly until it is fully engaged within the hanger.
The urinal is flushed after each use by means of flush valve which is operated by button 114. A small quantity of water, typically a pint or less, will be admitted into the flush ring 100 and discharged directly into the bowl housed within the cover below the flush ring. The water is drawn from the supply within the toilet tank through the filter 122 and line 110 and into the flush ring due to the hydrostatic pressure that exists by virtue of the level of flush ring being located below the normal water level within the toilet tank. The reservoir 120 will maintain the "prime" of the line 110. The toilet tank will automatically replenish whatever water is lost due to flushing the urinal through the action of the float valve normally associated with the toilet tank. Odors are minimized because the urinal is covered when flushed. Odors are also prevented from flowing through discharge line 70 as it is normally looped adjacent the base of the toilet at 128 which will maintain a water seal preventing odors from passing upwardly from the sewer drain into the bowl.
After use, the bowl is returned to its stored position convenient for later use. The shape of the bowl 50 facilitates use both by males and females. An important aspect of the preferred embodiment is that the urinal does not require the toilet tank 14 to be flushed but rather only a small quantity of rinse water from the toilet tank is required. This is in contrast to normal toilet operation which normally uses between 11/2 and 5 gallons of water per flush, resulting in substantial water savings.
In FIG. 5, an alternate embodiment of the present invention is shown again in conjunction with a conventional toilet having a toilet tank 14 and toilet bowl 12. For convenience, the same reference numerals are used throughout to identify the same or similar elements. The urinal bowl 50 is constructed as has been previously described having general overall funnel configuration terminating at a handle 64 with an outlet at the lower end of the handle. A flexible discharge line 70 connects the outlet and, as an alternative to the adaptation shown in FIG. 1, extends beneath the toilet lid assembly 30 depending through the P-trap of the toilet and directly into the sewer line 26. In this manner, no plumbing connections are required. In addition, the hanger 80 is as has been described with reference to FIG. 1 with a modification that the hanger has a rear wall 85. The rear wall 85 includes one or more holes 132 so that the hanger may be secured to a fixture such as the bathroom wall adjacent the toilet. The hanger 80 is as has been described above, provided with an internal flush ring through which water may be admitted across a valve by actuation of button 114. The flush valve is connected to a water supply by means of a tee 155 interposed in the filler line. One outlet of the tee connects to water line 160 which is flexible tubing. The water line 160 extends upwardly adjacent the rear and side wall of the toilet tank and is connected to an inlet 162 in hanger 80 connected to the flush ring across the valve. The flush valve, when operated, will allow water to flow through the flush ring to be discharged downwardly along the interior surface of the bowl.
The device shown in FIGS. 1 to 5 may be stored in a non-use position within the hanger 80 which reduces the possibility of emission of odors and also presents an aesthetically acceptable appearance. The device may be flushed passively using water from the toilet bowl as described above or, as shown, may also be connected to a pressurized water source such as the filler line which provides a supply of water to the toilet tank. In contrast to normal toilet operation, a very small amount of water is utilized.
FIG. 6 illustrates another embodiment of the present invention and which is generally designated by the numeral 200. Urinal 200 is shown in conjunction with a conventional toilet having a tank 14 and bowl 12 as has been previously described. The urinal has a urinal bowl 202 in the general configuration as previously described with respect to FIG. 1. The bowl 202 is generally funnel shaped diverging downwardly to a handle section 211. The urinal bowl is removably supported by a hanger 210 having a mounting clip 212 which may be securable to the side of the toilet tank. Clip 212 may be adhesively secured to the toilet tank or may be secured by means of a suction cup or other conventional expedient. The clip includes a pair of arms 214 and 216 which are generally C-shaped and are adapted to engage and support the urinal bowl in the area above the handle 211. Flushing water is communicated to the urinal bowl and waste is carried from the urinal bowl by conduit 215. Conduit 215, as seen in FIG. 7, defines separate lines 220 and 222, for flushing water and waste disposal, respectively. Conduit 215 is split towards its distal end with line 220 connected to the water line at fitting 225. Line 222 is connected to the toilet at connection 226 which may be a quick connect coupling which communicates with the sewer past the toilet trap. Alternatively, flushing water supply may be provided to the urinal bowl 202 directly from the toilet tank as shown in FIG. 4.
The urinal bowl of FIG. 6 is shown in detail in FIGS. 8 and 9. A flush ring 230 extends interiorly of the bowl adjacent the upper edge of the bowl. The flush ring 230 is provided with a series of orifices 232 which direct rinse water downwardly along the interior surfaces of the bowl. The flush ring is received with annular rim 228 which has a rearwardly extending housing section 233. The cover 235 is configured in the general shape of the upper edge of the bowl and is pivotally secured at pivot 236 to the rear of the rim 228. An L-shaped handle 241 is secured to the rearward extension 242 of the bowl. When it is desired to use the device, the bowl is removed from the bracket 210, the user grasping the device at the handle 211 with one hand and with the other pivoting the cover 235 to the open position shown in dotted in FIG. 8 placing the device in a use position. When the use of the device is completed, the device may be returned to the bracket 210 and the cover closed. The bowl is re-used by actuation of flush valve 245. Depressing plunger 241 will open valve 245 against spring 249 admitting water to the flush ring from line 220. Fluid is discharged from the bowl across grate 251 into waste line 222 and to the sewer.
It will be obvious that the embodiment shown in FIGS. 6 to 9 may be mounted on a support 210 located on a wall or fixture adjacent the toilet instead of a location on the toilet tank as seen in FIG. 6. The device may also be hung at any convenient location by handle 241.
In FIG. 10, the urinal bowl 202 is constructed as has been described with reference to FIGS. 8 and 9 having a general funnel shape converging downwardly to a handle 211. The device is suspended from a bracket 212 positioned adjacent the toilet tank 14 and toilet bowl 12 next to a wash basin 250. The water and waste lines 220 and 222 are again housed within a single conduit 215. The distal ends of the conduit are separated into lines 220 and 222. Line 222 is connected to the waste line 252 at a location downstream of the trap 254. A conventional plumbing connection 255 is provided for this purpose. Similarly, water supply line 220 is connected to a tee 263 which connects the faucet of the wash basin to a conventional water supply line.
The device of FIGS. 8 and 9 also provide an automatic flushing cycle when the cover 235 is opened for use. The rear of the cover has a lever arm 260 which rotates to the position shown in dotted lines in FIG. 8 when the cover is opened. This brings the lever into engagement with cam 262 on plunger 242 causing the water valve to be opened. Closing the cover after use will allow the plunger to return to a non-actuated closed position.
FIGS. 11 through 14 show still another embodiment of the water saving urinal device of the present invention which is generally designated by the numeral 300. The device may be mounted on any surface adjacent a waste line and is shown mounted on wall 302 adjacent wash basin 304 which basin has a waste line 306 which connects to a sewer. The device 30 has a water-containing housing 310 which may be of any convenient shape but is shown as being generally rectangular in cross section and having side walls 312, 314, a rear wall 316, front wall 318 and a bottom wall 320 which define reservoir 325. A cover 322 extends across the upper surface of the housing 310. The cover 322 may include a hinged lid portion section 324 which may be pivoted upwardly to provide access to the water-containing reservoir 325. As best seen in FIG. 12, reservoir 325 may be manually filled by lifting cover 324 and transferring water from a nearby source such as a basin faucet by use of a cup or container. Alternatively, as illustrated in FIG. 13A, reservoir 325 may be directly connected to a water source across a fill valve 330 which has an actuator 331 which may be manually depressed against spring 332 to align inlet port 314 with the water supply connected to fitting 335. Alternately, valve 330 may be a conventional float type valve which will maintain a constant fluid level in the reservoir 325.
The housing has a pair of opposed depending flanges 340 and 342 extending along the opposite sides of the bottom wall 320. The flanges each have an inwardly extending leg 344 which defines rearwardly extending legs which form a hanger for the urinal bowl 350.
The urinal bowl 350 is shown as being generally funnel-shaped or conical having a drain outlet 352 at its lower end which is connected to a flexible drain line 354 which, in turn, is connected to the sewer 306 across a conventional trap 355. The connector 500 is described in detail hereafter. The upper edge of the urinal bowl has a peripheral lip 360 which is slidably engageable within the flanges 340 and 342. Thus, in the "parked" position, the bowl may be fully inserted beneath the reservoir housing and in the use-position may be withdrawn. The insertion, removal and use of the urinal bowl is facilitated by the forwardly extending tab 370 which may be conveniently grasped by the user.
FIG. 12 shows a cross section of the receptacle and a portion of bowl 350 with the bowl in the parked or engaged position. The water reservoir 325 contains a quantity of flushing water which may be distributed into the bowl by operating valve 380 by depressing button 382 located on the front of the housing. A chamber 381 is disposed within the housing below the water-containing reservoir 325. The chamber 381 is provided with one or more orifices 386 located in the bottom wall 320 which will serve to direct water to the interior wall of the funnelshaped bowl when it is engaged in a parked position. Depression of operator button 382 will move slide plate 396 rearwardly to bring orifices 392 in the slide plate in registry with orifices 386 in the plate 320. When the button is released, biasing spring 398 will return the slide plate to its normal non-actuated position. Water flowing into chamber 381 will be directly along the side walls of the bowl 350 by peripheral openings 397 in foraminous baffle plate 345.
FIG. 15 shows yet another embodiment of the present invention designated by the numeral 400. In this embodiment, housing 402 is of any convenient shape having a side wall 406, and a bottom wall 410. Flanges 412 extend downwardly from the side wall 406 at opposite sides to receive the urinal bowl 450 when it is in the parked position. The urinal bowl 450 may be generally funnel shaped or bowl-shaped as shown and communicates with an outlet fitting 420 and waste line 422 which may be connected to any suitable waste discharge location.
The housing 402 defines an internal water reservoir 425. A cover 426 extends over the reservoir and has a pivotal lid portion 428 which may be opened so that the reservoir may be manually filled with a flushing water supply. Alternately, as has been described with reference to FIG. 12A, the reservoir may be connected to a source of supply water across a suitable water supply valve.
A discharge chamber 428 is located below the water reservoir 425 and has a generally foraminous concave wall 430 which serves as a distributor for water released into the chamber 428. Orifices 431 are located along the opposite edges of wall 430 to direct water onto the interior walls of the subjacent urinal bowl 450.
The advantage of the embodiment shown in FIGS. 15 and 15A is that it will deliver pressurized fluid for rinsing and washing the bowl. This is accomplished by a pump assembly 451 which has a upwardly extending plunger 452 which terminates at an operating button 454 in the top wall 426. The plunger is upwardly biased by spring 455. The lower end of the plunger carries a small piston 460 which is received within the chamber 462. Chamber 462 communicates with delivery chamber 466. Delivery chamber 466 has an outlet port 468 which communicates with subjacent chamber 428 across port 469. Chamber 466 also communicates with reservoir 425 via passageway 470. A one-way check valve 471 allows flow from the reservoir 425 into the chamber 466. Similarly, a one-way check valve 472 allows flow from chamber 466 into subjacent chamber 428 when chamber 466 is pressurized sufficiently to open the check valve 472.
In operation, plunger 452 is operated by the user manually pushing down on button 454. Chamber 466 has been filled with fluid from chamber 425 via passageway 470. When plunger 452 is depressed, the fluid within chamber 466, being essentially non-compressible, will cause the valve 472 to open. Piston 460, as it is further depressed, will force fluid through port 469 to be distributed by plate 430 through orifices 431 peripherally arranged about the plate. This water will be passed along the interior walls of the urinal to the drain to flush and clean the urinal bowl.
As indicated above, as for example in FIG. 11, the system of the present invention may be connected to a suitable drain or sewer which allows the unit to be placed adjacent an existing sink or wash basin. Building codes of many areas often do not permit direct connection to a sewer waste line simply by drilling or tapping into the line. Accordingly, it may be necessary to use an approved connector for this purpose.
Turning to FIGS. 16 and 17, a connector is shown which is generally designated by the numeral 500 which may be used in connection with sewer pipes of several diameters. In most localities, sewer pipes have an OD of either 1.5" or 1.9". The connector 500 has a cylindrical main body section 502 which has an interior diameter which closely corresponds to a first lesser diameter, as for example the diameter of 1.5" OD pipe. This allows a 1.5" OD pipe to be engaged with the body section 502 as shown in FIG. 17. The abutting pipe sections 510 and 512 are slightly spaced apart when the connection is made. An angular connector 525 extends from the body section having a tapered end 526 and adjacent annular groove 528 so that a flexible waste line may be secured about the connector and held in place by an annular clamp positioned in an annular groove area 528.
The connector 500 is provided with opposite flange sections 530 and 532, each of which have an internal diameter which corresponds to or is slightly larger than a second, larger diameter, as for example the diameter of 1.9" OD pipe. Thus, if the connector is to be used with two sections of larger diameter pipe, the larger diameter pipe will be seated within the flanges 530, 532. If, on the other hand, the adaptor is to be inserted between a first, larger pipe section such as 1.9" OD pipe section 560 as shown in FIG. 16 and a smaller diameter pipe such as pipe section 562 as seen in FIG. 16, the adaptor accommodates such adjoining. Larger pipe section 560 is inserted within the flange section 532 and the smaller diameter pipe section 562 is inserted so that it is engaged within the body section 502. Preferably, the connector is made of a suitable plastic such as PVC and the connections can be made in conventional manner using PVC cement.
The device of the present invention may be mounted on either side of the toilet bowl at the preference of the user or dual devices may be provided at opposite sides of the bowl to provide "his" and "her" units. The device is easily used and may be grasped and adjusted to accommodate users of all ages and physical sizes. The construction, being primarily plastic, is durable, rust-resistant, inexpensive and may be provided as either an OEM product or as an aftermarket modification.
Other significant benefits result from use of the present invention. The use of the urinal will help avoid the male "seat down" controversy and, accordingly, will help in maintaining the toilet seat in a dry, sanitary condition. Soiling of carpet, flooring and clothing is less likely and embarrassing noise is also reduced.
Thus, will be seen from the foregoing that the present invention provides a unique, new and novel low-water volume urinal. The device is easy and convenient to install and may be mounted on either side of a conventional toilet. The device can be made from various materials but is preferably fabricated with the primary component such as the urinal bowl, housing, tubing and fittings fabricated from plastic for ease of maintenance. It is understood that the present embodiments as described above are to be considered as illustrative and not restrictive.
While the principles of the invention have been made clear in the illustrative embodiments set forth above, it will be obvious to those skilled in the art to make various modifications to the structure, arrangement, proportion, elements, materials and components used in the practice of the invention. To the extent that these various modifications do not depart from the spirit and scope of the appended claims, they are intended to be encompassed therein. | A uni-sex water conserving urinal which has a bowl which is engageable with a hanger on or near the toilet. A flush plate directs water into the bowl. In use, the bowl is detached and moved to a position of use which is permitted by the flexible waste and water supply line. The water supply is from a reservoir in the hanger. The reservoir may include a pump for manually pressurizing the flushing water. Flush water may be supplied by manually filling the reservoir or by connecting the reservoir across a valve to a water supply. A universal connector may be used to connect the waste line from the bowl into an existing drain line. | 4 |
REFERENCE TO RELATED APPLICATIONS
[0001] This application claims the benefit of U.S. Provisional applications having Ser. No. 60/532,420, filed Dec. 22, 2003, entitled “DEVICE FOR TREATING ENDOMETRIAL ABLATION”; Ser. No. 60/532,419, filed Dec. 22, 2003, entitled “EXPANDABLE MEMBER WITH CIRCULATING CHILLED LIQUID FOR GLOBAL ENDOMETRIAL ABLATION”; and Ser. No. 60/546,334, filed Feb. 20, 2004, entitled “CRYOSURGICAL DEVICES FOR ENDOMETRIAL ABLATION”, which applications are incorporated herein by reference in their entireties.
TECHNICAL FIELD
[0002] The present invention relates generally to cryosurgical devices for freezing and destroying biological tissues. More specifically, the invention relates to cryosurgical devices that can be used for freezing and thereby destroying endometrial tissues within the uterus of a female patient.
BACKGROUND OF THE INVENTION
[0003] Endometrial ablation is a common surgical procedure that is used to treat menorrhagia in women, which is typically accomplished through the application of either sufficiently hot or sufficiently cold temperatures to destroy the lining of the uterus. One type of procedure used for endometrial ablation involves the use of a device that rolls over the surface of the uterine wall while applying enough heat to destroy the endometrial tissue. While this type of procedure can be effective, it requires a significant amount of time and skill in manipulating the rolling device to ensure that the entire endometrium is destroyed.
[0004] Another type of procedure used for endometrial ablation also uses heat, but instead involves balloons or similar distensible bladders. These balloons are inserted into the uterus and inflated with a fluid until the balloon contacts the affected surfaces of the uterus. Fluid is then heated to an appropriate temperature to ablate or destroy the endometrium. Good surface contact is important to get complete coverage of the uterine lining. However, such coverage can be difficult due to temperature fluctuations and gradients along the surface of the balloon that can be caused by many factors, such as convective currents of the fluid within the balloon. To improve control of the fluid temperature within the balloon, various mechanical devices and systems have been used for circulating or agitating the heated fluid, such as through multiple fluid passageways, propellers within a lumen contained within the balloon, vibrating members, and electrical impulses. These mechanical devices or systems provide varying degrees of effectiveness, depending on the administrator of the procedure and the device itself. In addition, the movement of hot fluid into the balloon can sometimes cause discomfort or possible tissue damage to the vagina and opening of the cervix as heat is conducted through the walls of the catheter to which the balloon is attached.
[0005] Another group of procedures used for endometrial ablation involves the application of extremely low temperatures and is commonly referred to as cryosurgery. In the performance of cryosurgery, it is typical to use a cryosurgical application system designed to suitably freeze the target tissue. The abnormal or target cells to be destroyed are often surrounded by healthy tissue that should be left uninjured. Many of these systems use a probe with a particular shape and size that is therefore designed to contact a selected portion of the tissue that is to be treated without undesirably affecting any adjacent tissue or organs. In one particular application used to treat conditions of abnormal uterine bleeding, cryoablation instruments and techniques are used to freeze endometrial tissue, thereby destroying at least a portion of the endometrium or lining of the uterus, while leaving the remainder of the uterus undamaged. An example of a device that can be used for this type of cryoablation is the Her Option Cryoablation System, commercially available from American Medical Systems of Minnetonka, Minn. In this type of system, a rigid probe is provided with a very cold tip that freezes the endometrial tissue with which it comes in contact. Where such a probe is used, the remainder of the refrigeration system must be designed to provide adequate cooling, which involves lowering the operative portion of the probe to a desired temperature and having sufficient power or capacity to maintain the desired temperature for a given heat load. The entire system must be designed so that the operative portion of the probe can be placed at the location of the tissue to be frozen without having any undesirable effect on other organs or systems. For this reason, probes in these types of systems are often in the shape of an elongated tube with a rounded tip area at one end that can be positioned within the uterus for the cryoablation procedures. Other cryocooling surgical devices, components thereof, and surgical methods are disclosed in U.S. Pat. Nos. 5,275,595; 5,758,505; 5,787,715; 5,901,783; 5,910,104; 5,956,958; 6,035,657; 6,074,572; 6,151,901; 6,182,666; 6,237,355; 6,241,722; 6,270,494; 6,451,012; 6,471,217; 6,471,694; 6,475,212; 6,530,234; and 6,537,271, each of which is incorporated by reference in its entirety.
[0006] In many cases, the cold portion of an instrument or device is provided through the use of a Joule-Thompson refrigeration system. These refrigeration systems generally operate through the expansion of a high-pressure gas through an expansion element that includes some sort of a flow restrictor. The restriction of flow may be accomplished through the use of a small orifice, a narrow capillary tube, or some other sort of passage that is smaller than the supply source through which the high-pressure gas must move. Typically, the refrigeration system includes a source of high-pressure gas, a heat exchanger, an expansion element, a heat transfer element, and various tubes or conduits that allow movement of the gas from one component to another. The high-pressure gas passes through the heat exchanger to lower the gas temperature at least slightly, then the gas temperature is further lowered through the isenthalpic expansion of the gas as it passes through the expansion element. This expanded and cooled gas is exposed to the heat transfer element, where the gas can then absorb the heat that has been transferred from the environment.
[0007] In most systems, the cooling tip is designed or chosen to be small enough to easily be accurately positioned at the treatment area, which generally limits the technique to applying the cooling to a relatively small area with each placement of the probe. The entire process thus typically requires that the probe be positioned at least two or three times to ablate the entire target area, such as an entire uterine cavity. Each relocation of the probe requires repetition of the same cooling steps, which can be time consuming and requires multiple precise placements of the probe to guarantee that the entire area is adequately ablated.
[0008] With these cryosurgical techniques, it is typically desirable to insulate the shaft of a cryosurgical probe to prevent the unintentional freezing of tissue at locations along the length of the probe that may inadvertently or unavoidably come in contact with the probe shaft. One way these shafts are often insulated is to provide a vacuum space along the probe shaft. This method is sometimes ineffective because the level of the vacuum maintained in such a space can degrade over time due to the outgassing of metals, plastics, and braze joints. This outgassing can increase during sterilization procedures in which heat is applied to the probe. Thus, it is known to incorporate the insulation into a disposable sheath that can be disposed over a probe, as is described in U.S. Pat. No. 6,182,666 (Dobak III), for example, so that the disposable element is not subjected to repeated sterilization, but instead can be discarded without significant degradation of the insulation. This disposable sheath can be constructed of a thermally resistive material, such as a plastic, to inhibit heat transfer between the surrounding tissues and the probe that it covers.
[0009] There is, however, a need to provide a system and device for endometrial ablation using cryosurgical methods that improve the overall coverage of the endometrial surface for a range of uterine sizes and shapes while maintaining an appropriate depth of ablation. There is further a need for these systems and devices to be easily manipulated to the affected areas, while having the ability to quickly generate an appropriately sized cold area or ice ball within the uterus for ablation. In addition, these systems will desirably include an efficient heat exchanger that provides improved cooling power with a given amount of input energy.
SUMMARY OF THE INVENTION
[0010] The present invention provides systems of performing endometrial ablation using cryoablation techniques that include a heat exchanger that provides for efficient cooling of the fluid used for the processes. The heat exchanger is configured to be unobstructive to good fluid flow through the system while achieving a pressure drop within a certain range with a variety of fluids. The heat exchanger of the invention may be used in currently available systems, such as the Her Option Cryoablation System, commercially available from American Medical Systems of Minnetonka, Minn.
[0011] In one aspect of this invention, a cryoablation system for performing endometrial ablation is provided comprising an elongated tubular cannula having a proximal end, a distal end, and a longitudinal axis, an expandable balloon extending from the distal end of the cannula and fluidly connected to a source of heat transfer fluid by at least one fluid path, a pump for circulating the heat transfer fluid into and out of the balloon, a probe handle coupled to the proximal end of the cannula and in fluidic communication with the balloon through the cannula, and a heat exchanger for varying the temperature of the heat transfer fluid, wherein the heat exchanger is fluidly connected to a secondary refrigerant source, and wherein the heat exchanger comprises an outer tubular wall and a plurality of fins extending from the tubular wall toward the interior portion of the heat exchanger.
[0012] In another aspect of the invention, a cryoablation system is provided with a handle from which a cannula extends, a cooling tip at the distal end of the handle, and a heat exchanger, where the heat exchanger comprises an outer tubular wall and a plurality of fins extending from the tubular wall toward the interior portion of the heat exchanger.
BRIEF DESCRIPTION OF THE DRAWINGS
[0013] The present invention will be further explained with reference to the appended Figures, wherein like structure is referred to by like numerals throughout the several views, and wherein:
[0014] FIG. 1 is a front schematic view of a cryosurgical probe of the type that may be used in accordance with the cooling devices and methods of the present invention;
[0015] FIG. 2 is a cross-sectional front view of one embodiment of a cannula and probe tip system of a cryosurgical probe, including a heat exchanger that is located at an opposite end of a cannula from a balloon;
[0016] FIG. 3 is a cross-sectional front view of another embodiment of a cannula and probe tip system of the present invention, including a heat exchanger that is located within a cryosurgical balloon;
[0017] FIG. 4 is a cross-sectional view taken along section line A-A of FIG. 3 ;
[0018] FIG. 5 is a cross-sectional side view of a heat exchanger including multiple fins, in accordance with the invention;
[0019] FIG. 6 is a cross-sectional top view of a heat exchanger having one exemplary arrangement of fins;
[0020] FIG. 7 is a cross-sectional top view of a heat exchanger of the present invention having another arrangement of fins;
[0021] FIGS. 8-10 are perspective views of three exemplary heat exchanger fin configurations of the present invention;
[0022] FIG. 11 is a front schematic view of a cryosurgical probe of the invention, including a finned heat exchanger at the distal end of the cannula; and
[0023] FIG. 12 is an enlarged cross-sectional view of the circled portion of the probe of FIG. 11 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0024] Referring now to the Figures, wherein the components are labeled with like numerals throughout the several Figures, and initially to FIG. 1 , one configuration of a cryosurgical probe 10 that can be used for cryoablation of endometrial tissue in the uterus of a female patient is shown, in accordance with the present invention. The probe 10 generally includes a handle 12 , a hollow tubular cannula 14 , and a probe tip 16 . The handle 12 can be metallic to facilitate effective sealing of the components to minimize any gas or fluid leakage that might otherwise occur. The handle 12 can also be provided with insulating properties so that it is comfortable for the user to manipulate, such as may be provided by the inclusion of insulation (e.g., aerogel) in the handle or in the form of a vacuum space within the handle. Several components of the refrigeration system, such as a heat exchanger, can optionally be housed within the handle 12 , as will be discussed in further detail below. Other components may also be housed within the handle 12 , such as various auxiliary instruments to support items such as temperature sensors, heaters, illumination optics, viewing optics, laser optics, and ultrasonic transducers. A conduit 18 preferably extends from the end of the probe 10 opposite the probe tip 16 , which may contain tubing for refrigeration system materials, power cables for any electrical components, fiber optical cables to support illumination, viewing, and laser components, and the like.
[0025] The cannula 14 may include within its hollow opening other components of the refrigeration system, such as a high-pressure conduit to transport a high-pressure gas mixture from the handle 12 to the probe tip 16 and a low-pressure conduit to return the expanded gas mixture from the probe tip 16 back to the handle 12 . Other components of the refrigeration system, such as a Joule-Thompson expansion element, can be housed within the probe tip 16 . When a Joule-Thompson expansion element is used for the cryoablation procedures of the present invention, a probe tip or some element located near the probe tip preferably includes at least one small opening that allows passage of a pressurized gas, such as nitrous oxide or carbon dioxide from an inner channel to a space having a larger volumetric capacity. As the gas expands rapidly, it chills to temperatures that are sufficiently low to perform low-temperature surgical techniques. In cases where material flowing through the cannula 14 is at a low temperature, the cannula 14 is preferably designed to minimize heat transfer from the surrounding tissues to the cryogenic gas mixture and to also keep the cannula 14 from unintentionally freezing tissue that comes in contact with its outer surfaces. Thus, the cannula 14 can be formed of a thermally resistive material, such as a rigid plastic, or it can be formed of a metal having insulation provided internally or externally to inhibit heat transfer. The cannula 14 may be a rigid tube or it can be more flexible and shaped differently than shown and/or vary in shape and size along its length.
[0026] FIG. 1 illustrates the probe tip 16 as generally including an elongated tube with a rounded tip portion, but it may instead be provided in a number of different forms in accordance with the present invention, as will be discussed in further detail below. As referred to herein, the term “probe tip” is generally intended to refer to the portion of the cryogenic probe device that extends from the end of a cannula that is opposite the fluid supply end of the cannula. Typically, this is the portion of the probe device that performs the actual cryogenic treatment. One exemplary embodiment of a probe tip of the invention generally includes the addition of a balloon with circulating fluid and local cooling through an elongated cannula. In particular, the balloon includes an intermediary heat transfer fluid that distributes cooling from the probe tip to the uterine wall. To use this type of probe tip, the balloon is inserted in its deflated state into the uterus through the cervix. The balloon is then filled with a heat transfer fluid to expand the balloon within the uterine cavity to contact the uterine wall. Preferably, the amount of pressure used is minimized so as to not put unnecessary amounts of pressure on the uterus. Sensors may be provided to measure the temperature and pressure of the fluid within the balloon. Preferably, the internal configuration of the probe tip is designed to maximize the cooling power and lower the temperature of the probe tip during the procedure. In addition, the balloon preferably fully encloses the probe tip. This design may further include a sheath that at least partially covers and contains the balloon in its collapsed position during insertion of the device, after which the sheath can be withdrawn or slid in a direction away from the balloon to thereby release balloon and allow it to expand outwardly to contact the uterine walls. The sheath may further be provided with insulating properties so that it can provide control of the freeze length when it is slid along the length of the extension relative to the balloon.
[0027] The balloon embodiment of the probe tip described above may further optionally include insulated lines through which relatively cold fluid can circulate to and from a console that provides the refrigerant. That is, the refrigerant can be cooled to therapeutic temperatures within the console rather than being cooled locally within the uterus. This system consists generally of a hand piece, a balloon, various sensors, fluid lines, and a coupling to the console. A cooler, valves, pumps, and reservoirs may be housed within the console. The console may also have the ability to supply the balloon with warm heat transfer fluid to allow thawing of tissue subsequent to freezing and to allow easier removal of the probe. Thus, the console includes the necessary internal cooler and fluid handling circuitry for it to perform as a generator of warm or chilled heat transfer fluid. The system is preferably also provided with a control system to regulate the flow of heat transfer fluid to and from the balloon and to control the pressure within the balloon. When the temperature of the refrigerant is lowered at a component outside the uterus, it is further preferred that an optionally provided sheath have insulating properties to keep the cooling portion of the tip from ablating the cervical canal when the probe is being inserted through the cervix to the uterus.
[0028] One preferred embodiment of a cannula and probe tip system of the type generally described above (i.e., a system including a balloon) is illustrated in FIG. 2 , which includes an elongated cannula that is truncated for illustration purposes, with the addition of a balloon at its distal end. The portion of the probe tip shown below the broken line in this embodiment basically represents the end portion of a cannula with a balloon attached to its outer surface, where the distance from the balloon to the handle or control portion of the device can vary widely, depending on the desired configuration of the device. In most cases, the length of the cannula will be considerably longer than the length of the balloon, although it is possible that the cannula is relatively short. In this particular embodiment, a cannula and probe tip system 20 includes a cryoprobe tip 22 , a heat exchanger 24 , a fluid pump 26 , and a balloon 28 attached to the end of a cannula 30 . This system is configured so that the cryofluid will be cooled outside the uterus, then transported to the uterine cavity when the balloon is positioned therein. Because the fluid will be extremely cold when transported through the cannula 30 , the cannula 30 and other components that carry the cold fluid will preferably be insulated to prevent unintentional freezing of tissues that come in contact with these components. The cannula 30 may be a rigid tubular portion, or may alternatively be made of a flexible material, where the upper portion of the system is then preferably located within a console.
[0029] The balloon 28 is shown in this figure in its deployed or partially expanded condition. It is noted that the system 20 may include a moveable sheath (not shown) that extends along at least a portion of the length of the cannula 30 . In order to achieve this inflated or partially inflated condition, a volume of fluid is provided to the balloon 28 until it is inflated to the desired size and is at least slightly pressurized. The fluid provided to the balloon 28 may be provided by a portable tank that can provide fluid under pressure, or may be connected to a relatively constant source of fluid that is compressed on site and provided through a supply line.
[0030] The system 20 further includes an elongated tube 32 that extends generally from the cryoprobe tip 22 , through the cannula 30 , and into the balloon 28 . The tube 32 has a first end 34 and a second end 36 , where the tube 32 is wider at its first end 34 than at its second end 36 . In addition, this end 34 is illustrated as being positioned in the handle of the probe, or at some other place spaced at a distance from the balloon. The end 34 is thus positioned near the location within the probe where the fluid within the cryoprobe tip is cooled by Joule-Thompson expansion. At its first end 34 , the tube 32 surrounds a portion of the cryoprobe tip 22 , which is the area where heat transfer between fluids occurs. The second end 36 of the tube 32 is open to the interior of the balloon 28 . In this way, fluid that exits the second end 36 of the tube 32 and enters the balloon 28 will be forced back toward the cryoprobe tip 22 by the pump 26 . When the fluid circulates to the first end 34 , it is forced back into the space between the cryoprobe tip and the tube 32 and into the area of the heat exchanger 24 . That is, the top portion of the cannula 30 closest to the first end 34 is the portion that is included as part of the heat exchanger The heat exchanger 24 includes at least one fin (not visible in this view) that extends from the interior wall of the elongated tube 32 toward the center of the device. The fin or fins help to increase the heat transfer rate of the fluid by increasing the surface area across which convection occurs. The thermal conductivity of the fin material has a strong effect on the temperature distribution along each fin and therefore influences the degree to which the heat transfer rate is enhanced. Thus, any fins that are included in the heat exchanger 24 will preferably be designed and configured to increase the efficiency of changing the temperature of the fluid that is circulated through the balloon, cannula, and other components of the system 20 . The fluid within the cryoprobe tip 22 is cooled through Joule-Thompson expansion. The second fluid is cooled in the heat exchanger by the extremely cold temperature of the first fluid in the cryoprobe 22 , and then delivered to the balloon 28 by way of the closed loop pumping circuit, as shown. This heat exchange process will thereby cool the second fluid to a predetermined temperature necessary for cryoablation.
[0031] FIGS. 3 and 4 illustrate another embodiment of a cryosurgical probe tip and balloon system 50 that generally includes an elongated cannula 52 having a sheath 54 that extends along at least a portion of the length of the cannula 52 , and a balloon 56 attached at one end of the cannula 52 . In this embodiment, the fluid is cooled within the balloon itself, so there is no need to transport the extremely cold fluid through an elongated cannula to the uterine cavity. One preferred method of performing cryoablation in accordance with the invention includes inflating the balloon 56 with a fluid that is relatively warm until it is contacting all of the uterine surfaces that need to be ablated. The balloon 56 is preferably at least slightly pressurized at this point. The warm fluid within the balloon 56 is then replaced with cold fluid through the use of a heat exchanger 58 , as described below. Once the fluid reaches its low cryoablation temperature, the endometrium is frozen to the desired thickness. The cold fluid is then replaced with warm fluid, which can again be accomplished through the use of the heat exchanger 58 , until the balloon 56 is sufficiently de-iced to allow it to break free of the frozen tissue. The balloon 56 can then be allowed to collapse and optionally be compressed again within a sheath for removal of the probe from the patient.
[0032] The system 50 preferably includes a heat exchanger 58 that operates with the use of a primary refrigeration circuit containing a first fluid and a secondary refrigeration circuit containing a second fluid, where both fluids simultaneously circulate through the heat exchanger to change the temperature of the fluids until a desired temperature of one or both fluids is achieved. The first fluid is provided through the cannula to a cryoprobe tip 60 where it is cooled through Joule-Thompson expansion. The second fluid is provided as a warm fluid to the balloon through a separate fluid path. In this case, the heat exchanger is preferably at least small enough to fit through the cervical canal, along with the balloon, cannula, and any other attached components. Because the cooling of the fluid within the balloon occurs more directly when the heat exchanger is located within the balloon, the cooling process can be comparatively quicker and can require less insulation of the other components of the device.
[0033] The heat exchanger 58 is also illustrated in FIG. 4 , which better illustrates multiple fins 68 extending from the interior wall of the elongated tube toward the center of the device. The fins 68 help to increase the heat transfer rate of the fluid by increasing the surface area across which convection occurs. Thus, any fins 68 that are included in the heat exchanger 58 will preferably increase the efficiency of changing the temperature of the fluid that is circulated through the balloon, cannula, and other components of the system 50 . The fins 68 that are used in the heat exchangers of the present invention may have a wide variety of shapes, sizes, and configurations. For example, as shown in FIG. 4 , the heat exchanger has eight fins 68 that are generally triangular in shape when viewed from the top. At least a slight gap is provided between each of the fins 68 so that the fluid flow through the device is not substantially obstructed.
[0034] A wide variety of designs and configurations are contemplated for the fins used in the heat exchanger of the present invention; however, some operating features should preferably be considered in the selection of a particular fin design to provide an efficient heat exchanger that does not detrimentally impact the operation of the cryosurgical device. One consideration is that there should be sufficient gaps or spaces between adjacent fins so that the pressure drop across the fins is not undesirably high. That is, it is preferable that the same fluids can be used with the heat exchangers of the present invention that include fins as with known systems that do not include fins. Thus, the number, size, shape, and placement of the fins within the heat exchanger should all be considered in determining a configuration that maximizes the heat transfer gained by the fins (i.e., maximizing the surface area across which convection can occur), while not providing a detrimental obstruction of the fluid flow. Further, the effectiveness of the fin design should be calculated to determine whether the fins will provide the desired effectiveness, which is defined as the ratio of the fin heat transfer rate to the heat transfer rate that would exist without the fins. In many cases, the use of many thin, closely spaced fins will provide for more effective heat transfer than wide fins that are spaced further from each other. In addition, the materials from which the heat exchanger and fins are made preferably have a high thermal conductivity to increase the fin effectiveness.
[0035] FIG. 6 illustrates a top view of another exemplary design of a heat exchanger 90 of the invention. The heat exchanger 90 includes a plurality of extending fins 92 spaced apart from each other in a spoke-like arrangement around the periphery of the heat exchanger by an equal number of generally rectangular troughs or gaps 94 . Again, the size and spacing of the fins 92 and troughs 94 can vary from the illustration, such as by changing the number and size of the fins 92 and the number and size of the corresponding troughs 94 . The fins 92 preferably extend along the entire length of the heat exchanger 90 , although it is possible that the fins are discontinuous along the heat exchanger length. For one example, the heat exchanger 90 has twelve fins 92 , where each fin is oriented at an angle of 30 degrees from each adjacent fin. It is also understood that the fins do not necessarily need to be evenly spaced around the periphery of the heat exchanger.
[0036] FIG. 7 illustrates a top view of another exemplary design of a heat exchanger 100 that includes a plurality of extending fins 102 spaced apart from each other by an equal number of gaps or troughs 104 in a similar arrangement to that illustrated in FIG. 6 . In this embodiment, however, the troughs 104 are rounded at the base of the fins 102 , which provides for at least a slightly different flow pattern than if the troughs were squared off. FIGS. 8, 9 , and 10 are perspective views of three alternative designs of fins that can be used in a heat exchanger of the invention. In particular, FIG. 8 illustrates a straight fin 110 of uniform cross-section and FIG. 9 shows a straight fin 112 that tapers from its base to its tip (i.e., a nonuniform cross-section), both of which can extend along the length of the heat exchanger in a continuous manner, if desired. The fin 114 of FIG. 10 , however, extends in a pin or spike type of manner from a base portion 116 and thus cannot extend continuously along the length of the heat exchanger. Rather, a plurality of these types of fins 114 could be used along the length of the heat exchanger to gain the desired cooling effect.
[0037] A cross-sectional side view of an exemplary heat exchanger 80 is shown in FIG. 5 , which illustrates a plurality of fins 82 that extend continuously along the entire length of the heat exchanger 80 . However, the fins may instead be discontinuous along the length of the heat exchanger, thereby creating additional flow paths for the fluid as it moves through the heat exchanger and past the fins. Alternatively, some of the fins may be continuous while others are discontinuous within a single heat exchanger.
[0038] While the description of the heat exchanger with fins or extensions is described above relative to a system including a balloon for cryoablation, it is possible that the heat exchanger of the invention be used for other probe tip configurations that include circulation of fluid through a heat exchanger. Several examples of such probe tip configurations are described in the copending U.S. patent application of the present Assignee filed on even date herewith, having U.S. Ser. No. ______, entitled “CRYOSURGICAL DEVICES AND METHODS FOR ENDOMETRIAL ABLATION,” Attorney Docket No. AMS0048/US, which is incorporated herein by reference in its entirety. One such example of a probe tip is a multiple-fingered extension that extends from the cooling portion of the probe. The extension includes two or more distinct flexible elongated members that extend from the cooling portion of the probe. The extension may have a corresponding number of internal refrigerant flow tubes or passages, each with its own refrigerant flow. The fingers can each include a capillary tube extending from the end of an inner supply tube toward the ends of the fingers. The capillary tubes can carry refrigerant that is provided by the supply tube at an acceptable treatment temperature for performing the ablation procedure. With any of these multi-fingered probe extensions, a recuperative heat exchanger is preferably used for a primary refrigeration circuit to cool the fingers for the ablation process. This heat exchanger may be located within the control handle, or at some location between the control and refrigerant supply console and the system handle. Alternatively, the heat exchanger may be located within the cool tip portion of the probe. Thus, heat exchangers having internal fins, as described above, can be used with these embodiments to improve the efficiency of those systems.
[0039] Another example of a probe tip configuration that can utilize the finned heat exchangers of the present invention is illustrated in FIG. 11 . This figure illustrates a system 120 having the basic components of the Her Option Cryoablation System available from American Medical Systems, additionally including a finned heat exchanger 122 . FIG. 12 shows an enlarged view of the heat exchanger 122 of FIG. 11 , which includes a plurality of fins 124 that extend along the length of the heat exchanger 122 in the direction of its longitudinal axis. It is preferable that the heat exchanger 122 be designed and configured to improve the cooling power of the system by about 60-70 percent as compared to a system that does not include fins. This heat exchanger 122 can include any of the features and configurations of the heat exchanger and fins described herein relative to other systems that include a finned heat exchanger.
[0040] The heat transfer fluids used in accordance with the present invention may include a variety of fluids that can provide the necessary cooling and heating of the tip of the device. The fluid is preferably biocompatible so that any unintentional fluid leaks would not be dangerous to the patient. Exemplary fluids include a hydrofluorocarbon fluid, such as Dupont Vertrel XF, which is commercially available from DuPont Fluorochemicals of Wilmington, Del.; a 1-mehosyheptafluoropropane, such as Novec HFE-7000, which is commercially available from the 3M Company of St. Paul, Minn.; a perflurocarbon or perfluorohexane, such as F2 Chemicals Flutec T14 (PF-I-hexane) or PP1 (PF-n-hexane) or combination, which is commercially available from F2 Chemicals Ltd. of the United Kingdom; ethyl alcohol (ethanol) (e.g., alcohol denatured with IPA and MeOH), which is commercially available from Spectrum Laboratory Products Inc. of Gardena, Calif.; a dimethyl polysiloxane, such as Dow Chemicals Syltherm XLT, which is commercially available from the Dow Chemical Company of Midland, Mich.; an aromatic hydrocarbon, such as Dynelene MV, which is commercially available from Dynalene Heat Transfer Fluids of Whitehall, Pa.; and propylene glycol, which is commercially available from Mallinckrodt Baker, Inc., of Phillipsburg, N.J. With these types of heat transfer fluids, the balloon or device in which the fluid is held is preferably made from either a polyurethane or silicone material.
[0041] In one particularly preferred embodiment, hydrochlorofluorocarbons (HCFC's), such as Asahiklin AK-225 or AK-225 g (hereinafter referred to as “AK-225”), which are commercially available from the Asahi Glass Co., Ltd. (Chemicals Americas, Inc.), of Tokyo, Japan, can be used as the heat transfer fluid, such as the fluid used to inflate the balloon. In this case, the balloon or device in which the fluid is held is preferably made from a polyurethane material, but may be made from other materials that can stretch to conform to the shape of the cavity in which it is inserted when filled with pressurized fluid, such as silicone, urethane, PET, and the like. The balloon should also have lubricous surface properties which prevent the balloon from sticking to itself and also allow it to easily slide over the uterine wall to allow uniform contact with the endometrium when inflated. Preferably, the balloon material should be relatively thin to minimize the thermal conduction losses due to heat transfer that can occur with balloons having a relatively large thickness, such as greater than about 0.05 mm for example. In addition, the balloon material should not crack or otherwise degrade when subjected to the extremely cold temperatures required for the cryoablation procedure and the balloon material should be compatible with the heat transfer fluid.
[0042] However, it is understood that fluids having similar properties to that of AK-225 may also be used as the heat transfer fluid, such as a fluid having a low vapor pressure at room temperature, a fluid having a freezing point that is preferably lower than about −110 degrees C. and a boiling point that is greater than about 50 degrees C., and more preferably has a freezing point that is lower than about −130 degrees C. and a boiling point that is greater than about 60 degrees C. In any case, it is preferred that the boiling point be at least above room temperature so that the fluid remains a fluid and does not vaporize when subjected to temperatures near room temperature. The heat transfer material preferably also has a relatively low viscosity over the entire operating temperature range to avoid large pressure drops, particularly when the material is exiting the balloon as this may generate uncomfortably high pressure within the uterus. The fluid is also preferably chemically inert to prevent degradation of the balloon, fluid lines, valves, seals, and other system components. In order to allow electrical isolation of the patient from the ground, the fluid is preferably not conductive. Further the heat transfer fluid is preferably chemically stable to allow storage for long periods and sterilization if necessary by methods of heat and gamma irradiation, for example. It is also preferably not flammable, not at risk of degrading into flammable or toxic compounds if exposed to electricity or high temperatures, and is both biocompatible and environmentally friendly.
[0043] Fluids used in the balloon, such as AK-225, are particular advantageous in accordance with the devices and methods of the present invention because it can remain in its liquid state when subjected to the operating conditions of the system. That is, the fluid preferably remains a liquid even at extremely low temperatures to provide better heat transfer to the patient. This type of fluid is able to cause a desired range of about 5 mm to about 7 mm of ablated tissue thickness to reach a temperature of about −20 degrees C. (which is well above its freezing point) at its outside edge, which is sufficient for ablation under many circumstances. In addition, the fluid used in the balloon preferably also remains a liquid within the balloon to provide a more uniform transfer of cooling to the tissue in contact with the balloon. It is further desirable that the fluid remains a liquid at room temperature and at the highest operating temperatures inside the system, thereby facilitating low pressure circulation of the fluid, ease of fluid handling and safety from a lack of significantly pressurized components in the fluid circuit.
[0044] Any of the embodiments of a probe tip discussed above may optionally include some type of disposable protective barrier or layer that can slip over the portion of the device that will be inserted into the patient. Since the protective layer can be removed and discarded after the procedure is complete, the cleaning and sterilization of the probe tip between procedures can be minimized or eliminated and the tip can be used to perform multiple surgeries. The protective layer is preferably provided to be as thin as possible in order to not interfere with the cooling of the tissue that is to be ablated, but thick enough that it does not tear during the insertion of the probe into the patient or during the ablation process. In cases where the probe tip includes multiple fingers or extensions, the protective layer may include individual tips for each of the multiple fingers, or may include a single protective layer or cover that covers all of the multiple fingers. The same or similar materials and designs as the balloons described above can also be used for the disposable protective barriers of the probe tip, if desired.
[0045] The probe tips described above and the devices to which they are attached can be designed and manufactured as a permanent part of the device such that once the device can no longer perform the desired surgical procedure, the entire device will be discarded. This may involve few or many uses of the equipment, depending on the device and the operating conditions in which it is used. For example, the use of protective covers can extend the life of the equipment. However, it is contemplated in accordance with the present invention that the probe tips used with a particular device instead be removable and replaceable in a “modular” type of system that allows the breaking of the refrigerant circuit to accept multiple probe tips of the same or different types. In this case, the probe tips could be disposable, thereby eliminating the need to sterilize the devices after each use. A modular system of this type preferably includes valving and storage reservoirs used to recover the refrigerant from the probe tip prior to detachment and evacuation of the probe tip after attachment.
[0046] For one example, the modular system includes a gas mix compressor that is used to transfer refrigerant from the probe tip to a storage reservoir during the detachment of the probe tip. The probe tip is then isolated with valves and residual gas in the probe can be vented to the atmosphere. A vacuum pump can then be used to evacuate the air in the system before reattaching the same or a different probe tip. Refrigerant can then be reintroduced to the probe tip by opening or activating the valves that were used to isolate the probe tip during its detachment from the system.
[0047] The present invention has now been described with reference to several embodiments thereof. The entire disclosure of any patent or patent application identified herein is hereby incorporated by reference. The foregoing detailed description and examples have been given for clarity of understanding only. No unnecessary limitations are to be understood therefrom. It will be apparent to those skilled in the art that many changes can be made in the embodiments described without departing from the scope of the invention. Thus, the scope of the present invention should not be limited to the structures described herein, but only by the structures described by the language of the claims and the equivalents of those structures. | A cryoablation system for performing endometrial ablation comprising an elongated tubular cannula having a proximal end, a distal end, and a longitudinal axis, an expandable balloon extending from the distal end of the cannula and fluidly connected to a source of heat transfer fluid by at least one fluid path, a pump for circulating the heat transfer fluid into and out of the balloon, a probe handle coupled to the proximal end of the cannula and in fluidic communication with the balloon through the cannula, and a heat exchanger for varying the temperature of the heat transfer fluid, wherein the heat exchanger is fluidly connected to a secondary refrigerant source, and wherein the heat exchanger comprises an outer tubular wall and a plurality of fins extending from the tubular wall toward the interior portion of the heat exchanger. | 0 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to vehicle lights, and in particular to a multiple light system for watercraft.
2. Description of the Related Art
Light systems are well-known and various types have heretofore been devised for meeting the requirements of particular lighting applications. For example, vehicles of various types typically have lighting systems for specialized purposes associated with their operation. Such purposes can include collision avoidance, for which many vehicles carry running lights of various configurations so that they are clearly visible to other vehicles.
Such light systems may be required for vehicle operation. For example, maritime regulations, such as those promulgated by the U.S. Coast Guard, specify the location, size, output and color of watercraft running lights. Such regulations tend to provide a degree of uniformity in watercraft lighting whereby watercraft operators can more quickly recognize other watercraft at night and take appropriate measures to avoid colliding with them. Hence, by regulation watercraft operated at night are required to display a bow light with a red light on the port (left) side and a green light on the starboard (right) side so that observance of such a light from other watercraft provides an indication of the direction of travel.
Other types of watercraft lighting systems serve different purposes, e.g., to illuminate areas external to the watercraft. Heretofore, relatively high output lights have been provided on the bows of boats to function in a manner similar to headlights on a road vehicle. However, Coast Guard regulations restrict the use of such lights to avoid impairing the vision of other watercraft operators.
Search lights and floodlights have also been mounted on watercraft, but typically they are intended for more general purposes as opposed to illuminating the area directly ahead of a boat. Lighting can become important in docking a boat and in launching and retrieving a boat with a trailer at a loading ramp. In the case of recreational watercraft which are often trailered to and from the boat loading ramps at public marinas, retrieval operations onto trailers after dark are fairly common. However, problems can arise with docking and trailer-loading operations due to the inadequacies of most navigation lights in providing sufficient illumination. Such operations could often be accomplished more safely and efficiently with adequate bow lighting, provided such lighting could be activated independently of the bow navigational or running lights in order to comply with Coast Guard regulations and to avoid obscuring the visibility of the bow navigational light.
The bow areas of many boats can be limited in space for mounting additional equipment, such as lighting systems. For example, recreational watercraft often have trolling motors, individual seats for fishing, etc. mounted in the bow areas thereof. Moreover, such equipment may have to be removed in order to place a cover over a boat for protecting it during periods of non-use. For this reason the red/green bow navigational lights of many watercraft are often mounted on removable masts or standards to facilitate covering and storing the boats during periods of non-use.
Therefore, an effective watercraft docking light should not interfere with the boat navigation lights, should be out of the way of other equipment and should provide effective illumination of an area in front of the boat. The present invention address the aforementioned problems related to watercraft lighting systems. Heretofore there has not been available a multiple lighting system for watercraft with the advantages and features of the present invention.
SUMMARY OF THE INVENTION
In the practice of the present invention, a multiple light system is provided for mounting on the bow of a watercraft. The multiple light system includes a navigational light assembly with a mast or standard mounting a navigational light. An auxiliary light is mounted on the mast by a light mounting assembly which includes an extension bracket. The auxiliary light is electrically coupled to the mast-mounted navigation light and a switch is provided on the extension bracket for selectively disabling the auxiliary light.
OBJECTS AND ADVANTAGES OF THE INVENTION
The principles objects and advantages of the present invention include: providing a multiple light system; providing such a light system for watercraft; providing such a light system with a docking light adapted for mounting on an existing mast-mounted navigation light assembly; providing such a light system with an auxiliary light assembly which is adapted to be easily retrofit on an existing light assembly; providing such a light system wherein the auxiliary light is electrically connected to an existing light assembly; providing such a light system which facilitates docking operations; providing such a light system which facilitates-loading and unloading a watercraft with a trailer; providing such a light system which can be selectively disabled independently of the navigational light; providing such a light system wherein the auxiliary light can be positioned out of the way of other equipment; and providing such a light system which is economical to manufacture, efficient in operation and particularly well-adapted for the proposed usage thereof.
Other objects and advantages of this invention will become apparent from the following description taken in conjunction with the accompanying drawings wherein are set forth, by way of illustration and example, certain embodiments of this invention.
The drawings constitute a part of this specification and include exemplary embodiments of the present invention and illustrate various objects and features thereof.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is an upper, side perspective view of a multiple light system embodying the present invention, shown mounted on the bow of a boat.
FIG. 2 is a side elevational view thereof, particularly showing the electrical interconnection of a navigation light assembly and an auxiliary light.
FIG. 3 is a fragmentary, exploded, perspective view of the light system, particularly showing a light mounting assembly for mounting an auxiliary light.
FIG. 4 is an enlarged, fragmentary side elevational view thereof, particularly showing the connections of electrical leads to contacts of a light bulb.
FIG. 5 is a fragmentary, exploded perspective view of an electrical connection system for an alternative type of navigational light bulb.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
I. Introduction and Environment
As required, detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which may be embodied in various forms. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed structure.
Certain terminology will be used in the following description for convenience in reference only and will not be limiting. For example, the words "upwardly" , "downwardly", "rightwardly" and "leftwardly" will refer to directions in the drawings to which reference is made. The words "inwardly" and "outwardly" will refer to directions toward and away from, respectively, the geometric center of the embodiment being described and designated parts thereof. Said terminology will include the words specifically mentioned, derivatives thereof and words of a similar import.
Referring to the drawings in more detail, the reference numeral 2 generally designates a multiple light system embodying the present invention. The multiple light system 2 generally comprises a mast-mounted light assembly 4, a light mounting assembly 6 and an auxiliary or additional light 8.
The multiple light system 2 is shown mounted on a boat 3 near the bow 5 thereof, which can include a deck 7 with a light mast mounting plate 9, through which the multiple light system 2 can be inserted for connection to an electrical system of the boat 3.
II. Mast-Mounted Light Assembly 4
The mast-mounted light assembly 4 includes a tubular mast or standard 10 with a lower end 12 which can include an end plug 14 for connection to an electrical system of the boat 3 and an upper end 16 mounting a mast-mounted navigation light 18. The mast or standard 10 includes a slight bend at 20, but could also have a straight configuration.
The mast-mounted light 18 includes a housing 22 mounted on the mast or standard upper end 16 and mounting a lens 24 for directionally emitting light from a socket-type bulb 26 with electrical contacts 28a, 28b. The bulb 26 can be either a replacement for or a modification of a conventional socket-type bulb which is normally utilized in navigation lights such as that shown at 18. The mast-mounted light 18 can comprise a navigation or running light with the lens 24 being divided into a green (starboard) portion and a red (port) portion consistent with conventional maritime practice.
III. Light Mounting Assembly 6
The light mounting assembly 6 includes an extension bracket 30 with a generally rectilinear configuration having proximate and distal ends 32, 34, upper and lower surfaces 36a, 36b and opposite side edges 38.
A mast receiver 40 extends between the extension bracket surfaces 36a, 36b and is open at a slot 42 which extends from the mast receiver 40 to the bracket proximate end 32. A clamp bolt receiver 44 extends transversely through the extension bracket 30 between its side edges 38 and through the slot 42 intermediate the mast receiver 40 and the bracket proximate end 32. The receiver 44 receives a clamp bolt 46 which threadably mounts a clamp nut 48 for providing clamp means whereby the extension bracket 30 is slidably and rotatably mounted on the mast 10.
A switch receiver 50 extends through the extension bracket 30 intermediate the mast receiver 40 and the distal 34 end thereof. The switch receiver 50 includes a counterbore 52 open at the extension bracket lower surface 36b. A bolt receiver 54 is provided in proximity to the extension bracket 30 distal end 34 and extends between the bracket upper and lower surfaces 36a, 36b.
First and second electrical leads 56, 58 are electrically connected to the bulb electrical contacts 28a, 28b respectively (FIG. 4) and are provided with respective push-type electrical connectors 60 for disengagement of the electrical leads 56, 58 whereby the entire light mounting assembly 6 and the auxiliary light 8 can be separated from the mast 10.
A single pole, single throw (SPST) toggle switch 62 is provided in series with the second electrical lead 58 and includes a toggle extension 64 with male threads for receiving a toggle switch mounting nut 66 with the toggle extension 64 extending through the switch receiver 50 and the toggle switch mounting nut 66 received in the counterbore 52.
IV. Auxiliary Light 8
The auxiliary light 8 can be used as a docking light and for this purpose can comprise a halogen quartz bulb 72 mounted in a housing 74 and electrically connected to the leads 56, 58, the latter via the toggle switch 62. The auxiliary light 8 has a clevis 76 with a mounting bolt 78 descending downwardly therefrom and rotatably received in the bolt receiver 54. The bolt 78 mounts a washer 80 and threadably mounts a mounting nut 82. The housing 74 is mounted on the clevis 76 by an axle bolt 84 and an axle nut 86 which permit adjustment of the orientation of the auxiliary light 8 by rotation with respect to a horizontal axis extending coaxially through the axle bolt 84.
V. Installation and Operation
The bracket 30 can be installed on an existing mast-mounted light assembly. Alternatively, the entire light system 2 can comprise a single unit.
For purposes of retrofitting to an existing bow light, the mast-mounted light assembly 4 can be removed by extracting the mast 10 from the plate or socket 9. The extension bracket 30 can then be slid over the mast 10 for clamping thereto by means of the clamp bolt and nut 46, 48. The extension bracket 30 permits rotation on the mast 10 for providing illumination where needed, e.g., directly ahead, off to a side, back into the vessel, etc. Moreover, the light mounting assembly 6 can be vertically adjusted on the mast 10.
The mast-mounted housing 22 can be modified by drilling a hole 75 in a lower portion thereof for the leads 56, 58.
VI. Modified Electrical Leads for Connection to an Alternative Bulb
FIG. 5 shows an alternative bulb 88 with electrical contacts 90a, 90b on the ends thereof for conductive receipt in electrical conductors 92a, 92b respectively of an alternative embodiment, mast-mounted navigational light assembly. For connecting the auxiliary light 8 to the alternative bulb 88, first and second electrical leads 94, 96 are provided with end loops 98 which slide over the bulb contacts 90a, 90b for making electrical contact therewith. The leads 94, 96 terminate at electrical connectors 100 for connection to electrical connectors 60 as described above.
It will be appreciated that various other types of electrical connection and retrofit arrangements could be provided for adapting the multiple light system 2 of the present invention to a variety of existing navigation lights, or for providing an integral multiple light system with both navigation and docking light capabilities.
It is to be understood that while certain forms of the present invention have been illustrated and described herein, it is not to be limited to the specific forms or arrangement of parts described and shown. | A multiple light system is provided for watercraft and the like which combines navigation light and docking light capabilities. A navigation light is mounted on top of a mast which protrudes from the watercraft deck. An auxiliary light, which can comprise a docking light, is mounted on the mast by a mounting assembly. The auxiliary light draws electrical power from a bulb of the navigation light and can be independently disabled by means of a switch on the mounting bracket. | 1 |
RELATED APPLICATIONS
This application claims the priority of German Patent Application, Serial No. 10 2009 018 058.3, filed Apr. 21, 2009, pursuant to 35 U.S.C. 119(a)-(d), the content of which is incorporated herein by reference in its entirety as if fully set forth herein.
FIELD OF THE INVENTION
The invention relates to a circular comb for a combing machine for combing textile fibres.
BACKGROUND OF THE INVENTION
Combs for use in combing machines are known in the form of round combs from public prior use, at least one comb element, which is engaged with the fibres to be combed, being arranged on a base body. A comb, which has a plurality of comb elements along its entire periphery, is called a circular comb. The active combing region may be, in this case, 78°, 90°, 111°, 180° of the periphery of the surface line of the comb. Circular combs are also known, in which the entire surface line is taken up with comb elements, such as needles, needle strips, saw-tooth wire portions, comb teeth or saw-tooth stamped parts. These comb elements, which are per se preassembled, are also called bar tacks.
SUMMARY OF THE INVENTION
A bar tack thus has a plurality of saw-tooth stamped parts arranged one behind the other in the direction of a centre longitudinal axis of the base body or also toothed discs with teeth. The teeth wear because of their mechanical engagement in the fibres to be combed, so it is necessary for the bar tacks to be replaceable in design. For this purpose, various fastening devices are known:
Card clothings for flat lids of a carding machine are disclosed in DE 43 26 203 C1, EP 0 091 986 A1 and EP 0 322 472 A1, the card clothing consisting, similarly to a bar tack of a circular comb, of a plurality of saw-tooth wire strips arranged in parallel to one another. The individual saw-tooth wire strips are placed in a row on a base body and held by a positive connection by means of adjacent fastening strips. The lateral fastening of the saw-tooth wire strips on the base body can also take place by means of clamping, in other words by a non-positive connection. As EP 0 322 472 A1 shows, the individual saw-tooth wire strips can be repeatedly bent in the arrangement direction. The fastening of the card clothing on the cover of the carding machine also takes place by means of the fastening strips, which are pushed onto the cover.
A similar fastening system of toothed discs on a bar tack of a circular comb is known from DE 25 03 976 C3, the individual toothed discs of a bar tack being clamped by means of a spring clamp onto a bar section. The entire bar tack is screwed to the base body of the circular comb. This type of fastening of the bar tack on the base body is also known in principle from GB 274 698 and DE 30 05 399 A1, a better seat of the bar tacks on the base body being achieved, according to the latter, in that they additional have a clamping strip and are arranged therewith in a recess of the base body corresponding thereto.
Further configurations of clamping strips are known from DE 30 07 245 A1, EP 0 249 706 A2, EP 0 179 158 B1 and EP 0 839 934 A1, a screwing connection of the clamping strips in the operating state, in other words when the bar tack is pushed on, being accessible from the inner wall of the hollow cylindrical base body. This accessibility of the screw connections from the inner wall of the base body is limited. On the other hand, a clamping strip is positively held according to EP 1 523 591 B1 both in the base body and in the bar tack. The assembly and disassembly of this comb are very laborious.
Furthermore, various possibilities for positively connecting bar tacks in the form of tooth clothings on the base body of a round comb are described in EP 1 533 404 A1.
According to U.S. Pat. No. 4,716,629, the fastening of a bar tack in a base body takes place by means of a resilient clamping element, which may, for example, be configured as a slotted sleeve. The clamping element is inserted into a groove, which is formed by the base body and the bar tack and extends parallel to the centre longitudinal axis of the base body. The holding force of a clamp with a clamping element of this type is low. Moreover, an additional securing of the clamping element against unintentional release is necessary.
It therefore applies to all the fastening systems mentioned that an assembly and disassembly of the bar tack to or from the base body of the circular comb is only possible by laborious assembly and retrofitting operations. This takes place, for example, by means of numerous screwing operations of the clamping and fastening strips and/or by axially pushing them on in the direction of the centre longitudinal axis of the base body, causing long setting up times and therefore stoppage times of the combing machine.
Spring-like holding parts, which are rigidly connected to the base body of a circular comb and on which the bar tack is placed and held as a result of the resilient spring force, are known from EP 0 253 071 A2. The simplified assembly process is counteracted by a reduced mechanical holding force between the bar tack and the base body.
DE 10 2006 005 605 A1 discloses a device on a carder, wherein a clothing is held by a magnet. The translational speed of the carder is significantly reduced in comparison to the rotational speeds of the circular comb conventional in combing machines, so that the centrifugal forces acting on a bar tack of the circular comb, which quadratically depend on the rotational speed, are significantly greater than the negligible centrifugal forces acting on the carder. The magnetic holding force for the clothing of the carder is configured thereon to withstand the effects of force on the clothing caused by the process, these effects of force caused by the process being smaller than those which act on a bar tack of a circular comb when combing fibres.
It is therefore an object of the invention to design a circular comb for a combing machine in such a way that a bar tack can be directly and quickly connected to a base body, it being impossible to release the connection even with high loads.
This object is achieved according to the invention by a circular comb, in which the unlocking units are accessible from outside the combing region, in particular from at least one of the end faces, and an additional positive securing connection to secure the bar tacks is provided on the base body.
It was recognized according to the invention that a circular comb with a base body and a plurality of bar tacks connected thereto in a non-positive manner has unlocking units, which in each case comprise an unlocking device and an unlocking means, and a securing of the connection of the bar tacks to the base body against unintentional release is ensured by an additional positive connection. The bar tack can be released from the base body by actuating the unlocking device by means of the unlocking means, the unlocking process being facilitated, in particular because of the arrangement of the unlocking units outside a combing region, which is determined by the bar tacks, and, in particular on the end faces of the base body because of the good accessibility. Moreover, owing to the additional positive securing connection between the bar tack and the base body, a secured connection of the two components to one another is guaranteed in case, in the event of damage, the non-positive connection between the bar tack and the base body is not maintained. This is relevant, in particular, for circular combs, which are used at high rotational speeds of up to 500 min −1 and with a high comb load, so that a bar tack, which could possibly be released from the base body as a result of the very high force loads during combing operation, does not cause damage to the combing machine. A further advantage of the circular comb according to the invention is the uncomplicated configuration of the geometry of the base body, resulting in a reduction in its production costs, and therefore the production costs of the circular comb as a whole are reduced.
In a circular comb, in which the positive securing connection between one of the bar tacks and the base body in each case has a radial play, the positive securing connection between one of the bar tacks and the base body has radial play, so the positive connection only engages if the non-positive connection between the bar tack and base body is removed. The non-positive connection, which is present in the usual operation of the combing machine, is free of play.
Owing to the configuration of the radial play being smaller than a radial spacing of the bar tack non-positively connected to the base body from a machine wall of the combing machine, it is ensured that in the case of unintentional release of a bar tack from the base body during running operation of the combing machine, destruction of said combing machine by the released bar tack is avoided.
By using a bar tack and a fastening device designed such that assembly and disassembly of the bar tack on or from the base body substantially take place in the radial direction, it is possible to carry out the assembly and disassembly of the bar tack on or from the base body substantially in the radial direction in the combing machine. This dispenses with the withdrawal of the bar tack from the base body of the circular comb and therefore simplifies the necessary setting-up processes and therefore shortens the time outlay required for this. Moreover, a partial integration is possible in that a drive shaft of the combing machine and a base body, which is generally assembled on the drive shaft, are combined in the base body according to the invention. Production and assembly costs of the combing machine are therefore reduced. Moreover, the necessary space requirement in and on the combing machine is reduced when the unlocking means is assembled.
The use of an unlocking opening in the base body, which extends parallel to the centre longitudinal axis, as an unlocking device, and an unlocking pin, which can be moved to release the non-positive connection in the unlocking opening, as an unlocking means, makes possible a particularly rapid and easy unlocking of the bar tack from the base body by releasing the non-positive connection. Moreover, a very compact construction of an unlocking unit of this type is possible as the unlocking opening is integrated in the base body. Furthermore, the assembly and disassembly process between the bar tack and the base body is facilitated by using the radial play, the securing function of the positive connection being maintained at the same time.
With the design of a circular comb, in which the bar tack and the fastening device are designed such that a combing force acts as a closing force in a securing manner on the bar tack, a combing force active during combing operation acts as an additional securing mechanism on the non-positive connection of the fastening device to the base body, so the risk of unintentional unlocking of the fastening device and therefore a release of the bar tack is additionally reduced.
A fastening device comprising a profile strip and a leaf spring is distinguished by a compact and integrative mechanical structure.
A circular comb, in which each profile strip has a top piece with at least one laterally projecting nose to engage in undercut recesses of the bar tack, allows a secure and, at the same time, assemblable and disassemblable connection of the bar tack to the connection device.
Owing to the design of the fastening device and a bar tack, in which a T-shaped top piece with two laterally projecting noses, at least one nose, in the direction parallel to the centre longitudinal axis, having interruptions, which correspond with corresponding recesses of the bar tack for the assembly and disassembly thereof, assembly and disassembly of the bar tack on or from the base body take place easily and quickly. By displacing the bar tack parallel to a centre longitudinal axis of the base body by a certain amount of length, the bar tack can be inserted in or removed from the base body in the radial direction.
An assembly or disassembly process of a bar tack on the circular comb is additionally simplified with a fastening device comprising an L-shaped top piece with a laterally projecting nose.
With a circular comb, in which the leaf spring, to non-positively connect the bar tacks and base body, is held with a first spring part region in a receiving groove of the profile strip and rests with a second spring part region on a shoulder of a fastening groove of the base body, the non-positive connection of the bar tack and base body is produced by a prestressed leaf spring. The resulting holding force of the bar tack on the base body can be adjusted by adaptation of the leaf spring.
A fastening device, in which each profile strip has an T-shaped base with a contact face provided on a T-shaped side projection, wherein the contact face, to form the positive securing connection, can rest on the leaf spring and therefore indirectly also on the shoulder of the fastening groove and wherein the radial play is determined by the design of the contact face, the leaf spring and the fastening groove, allows the use of the radial play by unlocking the non-positive connection of the bar tack in the base body for disassembly.
A circular comb, in which the unlocking pin is rotatably arranged in the unlocking opening and the contour of the cross-sectional face of the unlocking pin running perpendicular to the centre longitudinal axis is not round, allows a simple unlocking process in that the unlocking pin is inserted in the unlocking opening and rotated about a longitudinal axis of the unlocking pin.
A fastening device, in which the fastening device is a rod-shaped magnet, the non-positive connection between the bar tack and the base body being provided by the magnetic force of the magnet, allows very good integration into the base body. Moreover, the effect of force on the holding force of the bar tack on the base body is integrated in the fastening device. The magnetic holding force of the fastening device can be influenced by the design thereof.
A fastening device, in which the magnet is a permanent magnet, ensures a secure and lasting holding force on the bar tack.
By using a fastening device, in which the magnet is an electromagnet, the magnetic effect of which can be activated and deactivated by means of a switch, the effect of force on the bar tack, in particular for an assembly or disassembly process, can be interrupted and then reproduced.
A particularly compact structure of the circular comb is produced by an arrangement of the fastening device, in which the magnet is rigidly arranged in a fastening groove of the base body.
In a circular comb, in which each bar tack has a hook-like step, which, to form the positive securing connection, engages in a receiving opening of the fastening groove limited by a projection, the radial play being determined by a radial spacing provided in a non-positive connection between the projection and the hook-like step engaging below the projection, the bar tack is secured by the positive securing connection against unintentional release from the non-positive connection of the bar tack on the base body. In this case, the bar tack and the base body are designed in such a way that with an existing non-positive connection, a radial play is present between the bar tack and the base body, which facilitates the assembly and disassembly of the bar tack on or from the base body.
With a circular comb, in which the magnet has a C-shaped cross-section perpendicular to the centre longitudinal axis, the unlocking opening being formed by the magnet and the bar tack connected thereto, the unlocking opening is integrated into the structure of the circular comb and does not have to be introduced into the base body of the circular comb in an additional manufacturing step.
The use of an unlocking pin in a circular comb which is conical at least in portions allows rapid and direct unlocking of the bar tack from the base body by insertion of the unlocking pin parallel to a centre longitudinal axis of the base body into the unlocking opening.
The exchange process of a worn bar tack is simplified with a configuration of the fastening devices and the unlocking units, in which the fastening devices and the unlocking units are attached to the base body in such a way that they are connected, both during combing operation and also during assembly and disassembly of the bar tack on or from the base body, to said base body and can be brought, at least partially, into a loosened, but not completely separated assembly or disassembly state.
It is a further object of the invention to design a circular comb for a combing machine in such a way that a bar tack can be connected directly, rapidly and without additional aids to a base body.
This object is achieved according to the invention by a circular comb, in which the unlocking units are accessible from outside the combing region, in particular from at least one of the end faces, and the fastening devices and the unlocking units are attached to the base body in such a way that both during combing operation and also during assembly and disassembly of the bar tack on or from the base body, they are connected to the latter and can, at least partially, be brought into a loosened, but not completely separated assembly or disassembly state.
The advantageous configurations described above can also be used in such a circular comb.
It was recognized according to the invention that a circular comb with a base body and a plurality of bar tacks non-positively connected thereto has fastening devices and unlocking units, which in each case comprise an unlocking device and an unlocking means. Both the fastening devices and the unlocking units are releasably attached, in particular, to the base body and, to assemble and disassemble the bar tack to or from the base body, remain mounted thereon. They are attached to the base body in such a way that both during combing operation and during the assembly and disassembly of the bar tack on or from the base body, they remain connected thereto and can be brought, at least partially, into a loosened, but not completely separated assembly or disassembly state. As a result, an exchange process of a worn bar tack is simplified.
An unintentional release of the bar tack from the base body is prevented by a circular comb, in which an additional positive securing connection is provided to secure the bar tacks on the base body.
Embodiments of the invention will be described in more detail below with the aid of the drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 shows a side view of a circular comb with nine bar tacks fastened thereon in the peripheral direction;
FIGS. 2 and 3 show enlarged views of a fastening device shown in FIG. 1 according to a first embodiment, comprising a profile strip in the locked and unlocked state;
FIG. 4 shows a perspective view of a profile strip for use in a circular comb according to the first embodiment;
FIGS. 5 and 6 show views similar to FIGS. 2 and 3 of a fastening device according to a second embodiment of a circular comb;
FIGS. 7 and 8 show views similar to FIGS. 2 and 3 of a fastening device according to a third embodiment of a circular comb; and
FIG. 9 shows a view similar to FIGS. 2 , 5 and 7 of a fourth embodiment of a circular comb with a rod-shaped magnet as the fastening device.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
A circular comb 1 shown in FIG. 1 has a hollow cylindrical base body 2 with a centre longitudinal axis 3 , an outer peripheral surface 4 and two end faces 5 , of which only one is visible. The base body 2 is placed on a drive shaft 6 , which is also hollow cylindrical. It is also possible for the base body 2 to be driven directly, in other words without an additional drive shaft 6 . For this purpose, the base body 2 can be configured both as a hollow and as a solid shaft.
A total of nine bar tacks 9 fastened in each case by means of a fastening device 8 are attached to the base body 2 in the peripheral direction 7 . The bar tacks 9 define, with their axial extent parallel to the centre longitudinal axis 3 , a combing region of the circular comb.
Each fastening device 8 comprises a profile strip 10 and a leaf spring 11 , by means of which the respective bar tack 9 is fastened non-positively to the base body 2 . To unlock the non-positive connection, an unlocking means in the form of an unlocking pin 12 is used, which is arranged in an unlocking device, which extends as an unlocking opening 13 proceeding from at least one of the end faces 5 in the base body 2 parallel to the centre longitudinal axis 3 . Thus, the unlocking opening 13 is accessible from outside the combing region. To unlock the non-positive connection between the bar tack 9 and the base body 2 , the unlocking pin 12 can be introduced into the unlocking opening 13 and moved within the latter (here: rotated). During the combing operation of the circular comb 1 , for weight and safety reasons, no unlocking pin 12 is generally provided in the unlocking opening 13 .
Each bar tack 9 comprises a plurality of identically punched toothed discs, which are placed in a row one behind the other in the direction of the centre longitudinal axis 3 and connected to one another. Each toothed disc has a plurality of teeth 14 , which engage in the fibres to be combed. The bar tacks 9 are fastened to the base body 2 in such a way that each bar tack 9 has a radial spacing 15 from a machine wall 16 of a combing machine.
The fastening device 8 of the circular comb 1 is shown enlarged in FIGS. 2 and 3 . The fastening device 8 is inserted in a fastening groove 17 of the base body 2 . In this case, the profile strip 10 has a substantially double-T-shaped cross-sectional face, a T-shaped base 18 to positively receive the profile strip 10 being provided in the fastening groove 17 and a T-shaped top piece 19 with laterally projecting noses 20 being used to engage in an undercut recess 29 of the bar tack 9 .
The unlocking opening 13 is arranged adjacent to the fastening groove 17 and connected thereto, so the fastening device 8 can be actuated with the inserted unlocking pin 12 .
The base 18 , on a first T-side projection 18 a , has a contact face 21 , adjoined by a receiving groove 22 , in which the leaf spring 11 is held by a first spring part region 11 a . The fastening device 8 is inserted into the fastening groove 17 in such a way that the leaf spring 11 , which rests with a second spring part region 11 b on a shoulder 17 a of the fastening groove 17 formed by a first undercut, is prestressed, as the spring force of the leaf spring 11 in the radial direction 23 with respect to the centre longitudinal axis 3 is directed inwardly. The fastening device 8 is pressed inwardly in the radial direction 23 thereby, the prestressing of the leaf spring 11 resulting from an abutment of the bar tack 9 on contact regions 24 of the peripheral surface 4 .
As a result of the adjacent arrangement of the contact face 21 and the leaf spring 11 held in the receiving groove 22 , a radial play 25 of the fastening device 8 in the fastening groove 17 is produced. The size of the radial play 25 can be fixed by the design of the contact face 21 facing the shoulder 17 a , the leaf spring 11 and the fastening groove 17 . Since the contact face 21 has a bevel, the radial play 25 is additionally increased. When the base 18 lies with its contact surface 21 on the leaf spring 11 and therefore indirectly also on the shoulder 17 a , the radial play 25 becomes zero, so the positive securing connection is formed. The radial play 25 is smaller than the radial spacing 15 . This ensures that if the non-positive connection is released between the bar tack 9 and the base body 2 , no damage to the machine wall 16 and therefore the combing machine as a whole takes place. The bar tack 9 , apart from the non-positive connection, is also thereby positively connected to the base body 2 . With an active non-positive connection, in other words during normal operation of the combing machine, the positive securing connection does not engage, but has the radial play 25 .
The base 18 furthermore comprises a second T-side projection 18 b with a curvature 18 c to rest in the fastening groove 17 . On actuation of the unlocking pin 12 , the profile strip 10 can pivot about a pivot axis 18 d parallel to the centre longitudinal axis 3 by a certain angular amount, which is limited by the maximum radial play 25 . In this case, the profile strip 10 runs along the curvature 18 c in a second undercut of the fastening groove 17 in an unlocking direction. A combing force occurring during combing operation acts as an additional closing force. The bar tack 9 then acts on the profile strip 10 in such a way that the latter rolls with the curvature 18 c counter to the unlocking direction and is thus additionally held in the fastening groove 17 . The combing force is produced as the resultant of the individual combing forces on the individual teeth of the bar tack 9 . As a result, the non-positive connection between the bar tack 9 and the base body 2 is additionally secured and therefore increases the securing of the circular comb 1 against unintentional release of the bar tack 9 from the base body 2 .
The unlocking openings 13 reach at least up to at least one of the end faces 5 , so an actuation of the unlocking opening 13 with the unlocking pin 12 with a fully occupied circular comb is possible without providing accessibility of the base body 2 from its inside. As shown in FIG. 3 , the unlocking pin 12 inserted in the unlocking opening 13 has a contour, the cross-sectional face of which perpendicular to the centre longitudinal axis 3 is not round and comprises a flattened side 26 .
The unlocking of the bar tack 9 from the base body 2 will be described below with the aid of FIGS. 2 and 3 . Proceeding from the prestressed arrangement of the fastening device 8 and the bar tack 9 in the base body 2 according to FIG. 2 , the unlocking pin 12 is inserted into the unlocking opening 13 in such a way that its flattened side 26 is oriented parallel to a lower side 27 of the base 18 . The unlocking pin 12 is then rotated automatically or by hand, for example by means of a special tool about the longitudinal axis 28 thereof. Because of its non-round contour, the unlocking pin 12 comes to rest in the unlocking opening 13 and simultaneously on the lower side 27 , as a result of which the profile strip 10 is pressed in the radial direction 23 outwardly against the spring force of the leaf spring 11 (cf FIG. 3 ). In this state, the abutment of the top piece 19 with its noses 20 in contact flanks 30 a of an undercut recess 29 , which is substantially swallow tail-shaped, is dispensed with. Thus, gaps 30 are produced between the T-shaped top piece 19 of the profile strip 10 and the undercut recess 29 of the bar tack 9 in the regions of the noses 20 and the recess 29 on which there was previously contact, in the unlocked state. The gaps 30 allow a displacement of the bar tack 9 along the centre longitudinal axis 3 , as the mechanical holding force of the leaf spring 11 is removed.
FIG. 4 shows the profile strip 10 in a perspective view, whereby it becomes visible that the nose 20 of the T-shaped top piece 19 arranged above the contact face 21 has interruptions 37 in the direction parallel to the centre longitudinal axis 3 of the base body 2 . With recesses of the bar tack 9 corresponding to this, assembly and disassembly of the bar tack 9 on or from the base body 2 is facilitated in that the profile strip 10 in the unlocked state is displaced in the direction of the centre longitudinal axis 3 by the amount of the longitudinal extent of the interruptions 37 and can be removed in the radial direction 23 when the interruptions 37 overlap with the recesses of the bar tack 9 , which have the same longitudinal extent as the interruptions 37 . As a result the pushing of the bar tack 9 onto the profile strip 10 over the entire lengths thereof in the direction of the centre longitudinal axis 3 is avoided, so that, in particular, a necessary space requirement on the combing machine is reduced and the assembly and disassembly process can be accelerated.
FIGS. 5 and 6 show a further embodiment of a circular comb 1 . Components which correspond to those which have already been described above with reference to FIGS. 1 to 4 have the same reference numerals and will not be discussed again in detail.
An important difference of this embodiment from that described above is the design of the undercut recess 31 of the bar tack 32 . The recess 31 also has oblique contact flanks 33 , on which the noses 20 rest with an active non-positive connection between the bar tack 32 and the base body 2 . While a first side flank 34 is designed analogously to a swallow tail-shaped recess, a second side flank 35 is distinguished by a recess 36 , which extends in the bar tack 32 substantially in the peripheral direction 7 .
The disassembly process of the bar tack 32 from the base body 2 , which will be described below with the aid of FIG. 5 , is simplified with the recess 36 in the following manner:
By actuating the unlocking pin 12 in the unlocking opening 13 by rotation about its longitudinal axis 28 , the profile strip 10 , as described above, is raised outwardly in the radial direction 23 . This results in a tilting of the profile strip 10 in the fastening groove 17 of the base body 2 . Because of the special design of the undercut recess 31 , the bar tack 32 can be raised in the unlocked position of the fastening device 8 from the peripheral surface 4 of the base body 2 and disassembled in the radial direction 23 from the base body 2 . For this purpose, a nose 20 is pushed into the recess 36 , so the raising of the bar tack 32 and therefore the radial disassembly is firstly made possible.
FIGS. 7 and 8 show a further embodiment of a circular comb 1 . Components which correspond to those which have already been described above with reference to FIGS. 1 to 6 have the same reference numerals and will not be discussed again in detail.
An important difference of this embodiment from that described above is the design of the profile strip 10 a , which has an L-shaped top piece 19 a with only one projecting nose 20 .
Therefore, with the unlocked non-positive connection, the bar tack 32 a , which comprises a recess 29 a to receive the L-shaped top piece 19 a , can be directly withdrawn or lifted from the base body 2 . Furthermore, no bevel is provided on a contact face 21 a of the first T-side projection 18 a , as, because of the design of the top piece 19 a , a comparatively small radial play 25 a is sufficient to allow the unlocking process. The curvature on the second T-side projection 18 b is configured as a plateau 18 e . The nose 20 of the top piece 19 a is arranged on the same side of the profile strip 10 a as the plateau 18 e on the second T-side projection 18 b and therefore opposing the leaf spring 11 and the contact face 21 a adjacent thereto.
FIG. 9 shows a further configuration of a circular comb 1 . Components which correspond to those which have already been described above with reference to FIGS. 1 to 8 have the same reference numerals and will not be discussed again in detail.
The important difference from the above-described embodiments of a circular comb 1 is the configuration of the fastening device which is configured as a rod-shaped magnet 38 . The magnet 38 is arranged in a fastening groove 39 of a holding body 40 , the holding body 40 being fastened in a holding groove 41 of the base body 2 . The fastening can, for example, take place by means of screwing or gluing. It is also possible for no separate holding body to be provided and for the fastening groove 39 to be directly incorporated in the base body 2 .
The holding force of the non-positive connection between the bar tack 42 , which is produced from ferromagnetic material, and the base body 2 is produced by the magnetic force of the magnet 38 , which can be configured as a permanent magnet or as an electromagnet, so the magnetic effect thereof can be activated and deactivated by means of a switch.
The bar tack 42 has a hook-like step 43 , which engages in a receiving opening 45 of the fastening groove 39 delimited by a projection 44 . The step 43 cooperates here with the magnet 38 , which has a T-shaped cross-section perpendicular to the centre longitudinal axis 3 , in such a way that side faces 46 a and 46 b of the step 43 are in contact with end faces 47 a and 47 b of the magnet 38 . As a result, the unlocking opening 48 is formed. With an active non-positive connection between the magnet 38 and the bar tack 42 , a radial play 49 is present between the step 43 of the bar tack 42 and the projection 44 of the fastening groove 39 . When the magnetic holding force of the bar tack 42 is released, the latter is moved outwardly in the radial direction 23 , the step 43 coming to rest with its outside 50 on an inner face 51 of the projection 44 . By a corresponding design of the fastening groove 39 , in particular the projection 44 and the step 43 , the desired size of the radial play 49 can be fixed.
The magnet 38 is configured as a rod with a C-shaped cross-section perpendicular to the centre longitudinal axis 3 , one C-end face being inclined inwardly and forming one end face 47 a of the magnet 38 . Accordingly, the corresponding side face 46 a of the step 43 is also configured in an inclined manner, so the resulting combing force occurring during the combing process acts as an additional closing force on the non-positive connection between the bar tack 42 and the base body 2 . The incline of the end face 47 a and the side face 46 a form an inwardly directed guide, which pulls the bar tack 42 inwardly under the influence of the combing force and therefore presses it on the base body 2 .
An unlocking pin, not shown, which is conical at least in portions and can be inserted into the unlocking opening 48 parallel to the centre longitudinal axis 3 or moved back and forth, is used to unlock the bar tack 42 from the fastening groove 39 . As soon as the magnetic holding force of the magnet 38 on the step 43 has been overcome by a corresponding positioning of the unlocking pin, the bar tack 42 can be displaced because of the existing radial play 49 in the fastening groove 39 . As a result, a release of the abutment of the bar tack 42 in the contact regions 24 takes place and thus the possibility of tilting about a pivot axis 52 parallel to the centre longitudinal axis 3 .
In this unlocked state, the bar tack 42 can be disassembled substantially radially outwardly from the fastening groove 39 . A displacement in the direction of the centre longitudinal axis 3 is unnecessary for the assembly and disassembly of the bar tack 42 on or from the base body 2 . Assembly of the bar tack 42 on the base body 2 takes place analogously to disassembly by pivoting the bar tack 42 with its step 43 into the receiving opening 45 of the fastening groove 39 and subsequent application of the magnetic holding force by bringing the step 43 of the bar tack 42 and the magnet 38 into contact.
Apart from the fastening devices mentioned, further configurations are possible to apply the holding force to a bar tack:
When using a tension band made of elastomer as the unlocking means, which is inserted into the unlocking opening and exerts a clamping force on the bar tack, it could be stretched by tensile loading and therefore its cross-section reduced in the direction of the centre longitudinal axis, so a release of the non-positive connection could take place.
Moreover, the holding force on a bar tack could also be produced in that a negative pressure is produced in the unlocking opening and is eliminated to release the connection by means of a venting and aeration line provided for this.
Alternatively, unlocking means would also be possible, which are produced from a shape memory alloy, so a shape of the unlocking means can be adjusted as a function of a required clamping or non-clamping effect. This could take place, for example, by varying the cross-section perpendicular to the centre longitudinal axis. | Circular comb for a combing machine for combing textile fibers, comprising a base body with a center longitudinal axis, a peripheral surface and two end faces, a plurality of bar tacks, which are arranged on the peripheral surface of the base body and define a combing region of the circular comb, a plurality of fastening devices attached to the base body for the non-positive connection of one of the bar tacks in each case to the base body and unlocking units to release the non-positive connections, each unlocking unit having an unlocking device and an unlocking means to actuate the unlocking device, wherein the unlocking units are accessible from outside the combing region, in particular from at least one of the end faces, and an additional positive securing connection to secure the bar tacks is provided on the base body. | 3 |
BACKGROUND OF THE INVENTION
This invention relates to an apparatus for measuring photoelasticity and in particular to an optical system employing circular polarization for light of a wide wavelength region including the infrared region.
An apparatus disclosed in a Japanese reference "Oryoku Sokutei Ho (Stress Measuring Methods)" pp. 473-692, particularly pp. 492-503, published by Asakura Publishing Co., November 1964 has been known as an apparatus for measuring photoelasticity. However, the objects to be measured by means thereof are restricted to glass and plastic, which are transparent for the visible light region and white light (wavelength 400-760 nm) emitted by a tungsten lamp, D line (wavelength 589 nm) emitted by a natrium lamp, and light (wavelength 400-580 nm) emitted by a mercury lamp, that have been used as a light source therefor. In order to obtain the circular polarization necessary for the measurement of the photoelasticity, a quarter wavelength plate is used. Among the light sources described above, for the white light and the ultraviolet light, quarter wavelength plates for their center wavelength 580 nm and 490 nm, respectively, are used. Further, in the case where the light emitted by the light source is monochromatic as D line emitted by a natrium lamp, a phase shifter made of mica and corresponding to a wavelength of 147.25 nm is used as a quarter wavelength plate.
For this reason, when photoelasticity is measured by using a light source emitting light of wide wavelength region, it is difficult to obtain correctly circularly polarized light and measurement precision is not taken sufficiently into consideration. Further, in the case where a plurality of kinds of monochromatic light sources are used, they give rise to a problem similar to that of the light source stated above. As the result, an operation to interchange quarter wavelength plate in the course of a measurement is necessary, which complicates the measurement.
A stress measuring method, using the infrared photoelastic effect is disclosed in, for example, JP-A-No. 57-191504.
On the other hand, a catalog of an apparatus for measuring photoelasticity in the infrared region (Photolastic Inc. Model 501, Infrared polariscope) can be cited as a recent publication. However, this apparatus works only for a wavelength of 1.13 μm and doesn't meet the needs to measure photoelasticity by using a light source emitting light of wide wavelength region.
SUMMARY OF THE INVENTION
An object of this invention is to provide an apparatus for measuring photoelasticity permitting a continuous a measurement without interchange any element of the optical system, while using light of wide wavelength region.
Another object of this invention is to provide an apparatus for measuring photoelasticity having a simple construction of the optical system and providing correctly circularly polarized light.
This invention is characterized in that an apparatus for measuring photoelasticity using a light source emitting light of wide wavelength region or a plurality of kinds of monochromatic light sources and having a simple construction, which can be operated easily, by utilizing a Fresnel rhombic body (FIG. 6) acting as a quarter wavelength plate for light of wide wavelength region.
The Fresnel rhombic body is originated in a rhombohedron made of glass used by Fresnel, who has discovered the circular polarization. At present principally a quarter wavelength plate is used in order to obtain circularly polarized light from linearly polarized and the problem pointed out in the description of the prior art of this invention remains.
The Fresnel rhombic body (hereinbelow referred to as Fresnel rhomb) produces a phase shift corresponding to quarter wavelength, i.e. phase shift of 90 deg. by two total reflections, as indicated in FIG. 6. When linearly polarized light 3 enters a Fresnel rhomb 1, it is transformed into circularly polarized light 4 and emerges therefrom. Denoting the incident angle 2 in the Fresnel rhomb 1 by θ, the value of the incident angle θ depends on the wavelength of the used light and can be given by; ##EQU1## where n represents the refractive index of the material, of which the Fresnel rhomb is made. Since the refractive index depends on the wavelength of the light, the incident angle depends also on the wavelength. When the incident angle θ is calculated, supposing that the material, of which the Fresnel rhomb is made, is glass BK7 and that the wavelength of the used light is 589 nm (D line), θ=55°14'2" is obtained. When the phase shift in function of the wavelength is calculated for this incident angle of 55°14'2", the relationship between the wavelength and the phase shift, as indicated in FIG. 7, is obtained and it can be understood that it acts as a quarter wavelength plate for a wavelength region between 500 and 800 nm with a precision in phase difference of 90±0.5 deg.
This invention is characterized in that the characteristics of the Fresnel rhomb that variations in the refractive index due to variations in the wavelength are relatively small are applied to a device in practice.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view illustrating an embodiment of apparatuses for measuring photoelasticity according to this invention.
FIG. 2 is a scheme indicating the construction of the above embodiment.
FIG. 3 is a graph representing the phase shift produced by the Fresnel rhomb used in the above embodiment.
FIG. 4 is a scheme illustrating the construction of another embodiment of apparatuses for measuring photoelasticity according to this invention.
FIG. 5 is a graph representing the phase shift produced by the Fresnel rhomb used in the embodiment in FIG. 4.
FIG. 6 is a scheme illustrating a Fresnel's rhombic body, which can be used for this invention.
FIG. 7 is a graph representing the phase shift produced by the Fresnel rhomb in FIG. 6 with respect to the light incident thereto.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIG. 1 shows an apparatus for measuring photoelasticity, which is an embodiment of this invention, in which the light source part consists of a spectroscopic light source, which emits light for different wavelengths between 400 and 2600 nm, while analyzing spectroscopically light coming from a halogen lamp. The light of the relevant wavelength region corresponds to the regions from visible light to near infrared radiation. The optical system is composed of a troidal mirror 2-a, a polarizer 2-b consisting of a Glan-Taylor prism having an extinction ratio of 10 -5 a Fresnel rhomb 2-c, lenses 2-d and an analyzer 2-e consisting of a Glan-Taylor prism. The loading part is composed of a load element 3-a, which can effect tension, compression, bending and shearing with a maximum load of 500 kg, and a thermal chamber 3-b, which can set the temperature between -130° and 250° C. with a precision of ±1° C. The detector part is composed of a visible-infrared camera 4-a, which is sensible to light in the wavelength region between 400 and 2200 nm and a camera controller 4-b controlling the camera. The data processor calculates the principal stress difference σ 1 -σ 2 , the principal stress values σ 1 , σ 2 , the principal stress direction, and the shearing stress τ xy and is composed of a CPU 5-a, a television monitor 5-b, a console 5-c, a floppy disc drive 5-d, a digitizer 5-e, a video printer 5-f, and a plotter 5-g.
Hereinbelow this invention will be explained, by referring to FIG. 2 and the following illustrating the construction of different embodiments, where various items are indicated by new reference numerals.
In FIG. 2, a tungsten lamp is used as the light source 6, which emits white light (visible light λ=400-760 nm). Light 7 emitted by the light source 6 is transformed into linearly polarized light, passing through a polarizer 8 and further into circularly polarized light by a quarter wavelength plate 9 consisting of a Fresnel rhomb. It is further transformed into a parallel light beam having a large diameter through a concave lens 10 and a convex lens 11 and projected to a specimen to be measured 12. Light transmitted through the specimen to be measured 12 is collected by a convex lens 11' and a concave lens 10' and enters a television camera 14 through a quarter wavelength plate 9' consisting of a Fresnel rhomb and an analyzer 13. The signal (clear and dark) representing photoelastic fringes produced by the photoelastic effect on the specimen to be measured 12 is imaged on a television monitor through an amplifier 15 by the television camera 14. In this way a photoelastic measurement on the specimen to be measured is effected. In this case, the incident angle θ on the quarter wavelength plate consisting of a Fresnel rhomb is so set that the phase shift is 90±1 deg. for the visible light region. When the incident angle θ is calculated, supposing that the material, of which the Fresnel rhomb is made, is glass BK7 (trade name of an article commercialized by Schott Co. in West Germany) and that the refractive index n=1.521 for the wavelength λ=537 nm, θ=55°31'40" is obtained. The quarter wavelength plate consisting Fresnel rhomb having the incident angle described above of 55° 31'40" gives phase shifts for different wavelengths, as indicated in FIG. 3, and acts as a quarter wavelength plate producing a phase shift of 90±1 deg. for light of the wavelengths in the whole visible light region.
Now, another embodiment having the construction indicated in FIG. 4 will be explained. In FIG. 4, the light source 6 is composed of a halogen lamp 17 and a spectroscope separating light having an arbitrary wavelength by means of a diffraction grating 18 from the light emitted by the halogen lamp 17. In this way the apparatus for measuring photoelasticity according to this embodiment permits to effect photoelastic measurements by using arbitrary light in a wavelength region between 400 and 2000 nm (from visible light to near infrared light). In the construction illustrated in FIG. 4, the downstream from the polarizer 8 is basically identical to that described in the preceding embodiment, except that 2 kinds of Fresnel rhomb quarter wavelength plates are used, one for λ=400-760 nm (visible light) and the other for λ=760-2000 nm (near infrared radiation) and that the television camera 14' is sensitive to light of λ=400-2200 nm. The Fresnel rhomb quarter wavelength plates 9a and 9a' for λ=400-760 nm are made of glass BK7, similarly to that described in the preceding embodiment and the incident angle θ is 55° 31'40". On the other hand, for the Fresnel rhomb quarter wavelength plates 9b and 9b' for λ=760-2000 nm those, for which the incident angle θ giving a phase difference of 90° is 54°18'14" for a refractive index n=1.507 for a wavelength λ=1100 nm, when they are made of glass BK7, are used. FIG. 5 indicates a graph representing phase shifts vs. wavelength for the Fresnel rhomb quarter wavelength plates 9b, 9b' stated above. From FIG. 5 it can be understood that a phase shift of 90±1 deg. can be surely obtained for the wavelength region between 700 and 2000 nm. Consequently it is possible to effect photoelasticity measurements for a wide wavelength region between 400 and 2000 nm by mounting in the apparatus and using one of the two kinds of Fresnel quarter wavelength plates 9a, 9a' and 9b, 9b', as described in the preceding embodiment, depending on the wavelength of the light used.
A plurality of laser lights or a die laser can be used as the light source in the embodiments described above. Further, it is possible to ameliorate the precision on the phase shift by using more than 3 kinds of Fresnel rhombs. In addition, although Glan-Taylor prisms made of calcite having a high extinction ratio and absorbing no light for a wavelength region between 310 and 2300 nm were used for the polarizer 8 and the analyzer 13 in the above embodiments, Glan-Thomson prisms can be used instead thereof.
Furthermore it is required that the Fresnel rhombs are made of a material, whose refractive index n is not smaller than about 1.496, preferably, 1.49661. This is a result obtained from the calculation formula described previously under the condition to obtain a precise phase shift of 90° . Therefore the Fresnel rhombs indicated in Table 1 can be used arbitrarily, depending on the required precision on the phase shift. In the table the materials are identified by trade names of Schott Co. in West Germany, which are well known by those skilled in the art.
TABLE 1______________________________________ Materialrefractive index BK7 quartz SF6 BaSF7n.sub.D 1.517 1.458 1.805 1.702______________________________________visible incident 50°31'40" 51°25'06" 61°59'11" 60°44'06"region angle θ400-760 phase 89.1˜ 84.0˜ 89.4˜ 89.5˜nm shift 90.0 86.0 91.6 91.1 [deg]near in- incident 54°18'14" 51°25'06" 61°36'54" 60°21'28"frared angle θregion phase 89.0˜ 81.0˜ 89.4˜ 89.4˜760- shift 90.5 84.0 90.5 90.52000 nm [deg]______________________________________
Since, in the apparatus for measuring photoelasticity according to this invention, permitting to effect measurement of stress in specimens, a Fresnel rhomb quarter wavelength plate is used as a quarter wavelength plate constituting a part of the apparatus and it acts as a quarter wavelength plate for a wide wavelength region, it is possible to obtain purely circularly polarized light in photoelasticity measurements using light including components of wide wavelength region such as white light as the light source and thus to ameliorate measurement precision. Further, in the case where photoelasticity measurements are effected by using a plurality of monochromatic lights, it is not needed to prepare a number of quarter wavelength plates corresponding to various wavelengths and in this way it is possible to simplify the measurement apparatus and the measurement operation.
In addition an effect can be obtained to control products including not only Si monocrystal substrates but also polycrystalline Si semiconductor substrates, amorphous Si substrates, transparent objects, molded articles of opaque resins such as ABS resins or HIPS (High Impact Polystyrene) resins, and furthermore all sorts of thin films, whose thickness is about 1.0 μm, by visualizing stress therein. | An apparatus for measuring photoelasticity permitting to control mechanical stress applied to an elastic body, by visualizing phase differences of polarized light transmitted by the elastic body is disclosed. In such a prior art apparatus a quarter wavelength plate was used in order to obtain circularly polarized light. However, the precision of the circularly polarized light is worsened, when it works in a wide wavelength region. To the contrary, in an apparatus according to this invention, circularly polarized light is obtained by means of Fresnel's rhombic body. As the result good circularly polarized light can be obtained for a wide wavelength region from the visible region to the near infrared region and control of products including thin films and semiconductor substrates can be effected by visualizing mechanical stress therein. | 6 |
BACKGROUND OF THE INVENTION
This invention relates to a temporary receptacle for protecting printed material and the like from the elements, and, in particular, to a material repository that is formed by folding a single blank of suitable material along precut fold lines.
In many northern rural areas newspapers and the like are delivered by automobile to post mounted receptacles situated along the side of the road. During the winter months, the snowfall can become heavy and drifting and blowing of the snow presents a serious problem. Continual plowing of the roads oftentimes becomes necessary whereupon the receptacle is buried under drifts and cannot be located. Similarly, because of adverse weather conditions, plow operators may also inadvertently strike and break the receptacle post thereby rendering it unuseable. Accordingly, delivery people following in the wake of a plow may find no place to deposit their materials other than on the top of a snowbank. If the material is not quickly recovered by the subscriber, it can become watersoaked, blow away or even be buried in the snow. In any event, safe delivery of the printed material and the like under these conditions is oftentimes extremely difficult.
Also, many news dealers conduct promotional campaigns during which time free copies of their publications are delivered to perspective customers. Because of governmental regulations these materials cannot be deposited in existing mailboxes and it is usually necessary for the promotor to provide a temporary box for the duration of the campaign. Heretofore the expense of providing temporary boxes has been relatively high.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to insure the safe delivery of newspapers and other similar materials in snowbound rural regions.
It is a further object of the present invention to provide a temporary depository for newspapers and the like for use in snowbound rural regions.
Another object of the invention is to provide an inexpensive box that can be easily secured to an existing post for use during short promotional campaigns.
A still further object of the present invention is to provide a temporary delivery receptacle for printed material and the like which is formed from a relatively inexpensive board of foldable material.
Another object of the present invention is to provide a temporary newspaper container that is easily stored and which can be quickly erected in the field by a delivery person.
These and other objects of the present invention involve a receptacle for use in snowbound regions for temporarily housing printed material or the like. The receptacle is formed from a board of inexpensive foldable material that has been scored along predetermined fold lines so that it can be quickly and easily folded into a receptacle that includes a rectangular housing and a support standard for mounting the housing in a generally horizontal position. The bottom of the standard is provided with a pointed blade that can be easily inserted into a snowbank to securely hold the receptacle in an upright position or, alternatively, provide a means for temporarily securing the housing to an existing post.
BRIEF DESCRIPTION OF THE DRAWINGS
For a better understanding of these and other objects of the present invention, reference is had to the following detailed description of the invention that is to be read in conjunction with the associated drawings wherein:
FIG. 1 is a perspective view of the receptacle embodying the teachings of the present invention;
FIG. 2 is a top plan view of a blank of foldable material that has been scored to provide foldlines to enable the blank to be quickly folded into the receptacle illustrated in FIG. 1; and
FIG. 3 is a rear view of the present receptacle showing it secured in an upright position to a post.
DESCRIPTION OF THE INVENTION
With reference to the drawings, wherein like component parts are identified by like numbers, the present invention involves a receptacle for temporarily protecting printed material and the like from weather in order to safeguard the material between the time it is delivered and the time it is retrieved by the intended recipient. The receptacle, which is generally referenced 10 in FIG. 1, is made up of two main sections that include an elongated rectangular shaped housing 11 and a bladed standard 12 that depends downwardly from the housing.
As previously noted, the present invention involves a temporary receptacle for newsprint or the like that can be quickly and easily attached to an existing post or, in the case of a snowstorm, inserted into a snowdrift when the permanent box is buried or destroyed by snow removal equipment or an eratic driver. Preferably, the receptacle is formed from a single flat board of any suitable, inexpensive material that has been scored along predetermined fold lines to permit the board to be rapidly and accurately folded into a self-locking relatively strong structure capable of protecting printed matter and the like from the elements. A supply of blanks can be stored in a flat stack in the delivery person's motor vehicle and, when needed, simply folded and locked into the configuration shown in FIG. 1. In operation the standard can be inserted into a snowbank at the side of the road close to the recipient's location or alternatively secured to an existing post using staples, tacks, wires or the like.
The board can be made of any suitable foldable material such as a wide variety of relatively inexpensive paper or plastic boards that are presently commercially available. When a paperboard blank is used it is preferably treated with a thin coating of waterproof or resistant material that will serve to keep the board dry for a relatively long period of time despite adverse weather conditions. Such coatings are well known in the art and are readily available through suppliers of paperboard. In light of the fact that the present device is not intended to be used as a permanent installation, the use of a relatively inexpensive treated paperboard as a construction material is entirely satisfactory.
As shown in FIGS. 1-3, the housing of the present device is formed of four rectangular shaped panels of equal length. These include a bottom panel 20, two side panels 21 and 22 and a top panel 23. The lower edges of the two side panels are foldably connected or attached to the two side edges of the bottom panel by scoring a fold line in the board along the line of joinder between the adjacent panels. It should be noted at this point that all the fold lines which are used to connect the various panels of the present invention involve straight line folds that can be easily cut during the blank forming operation.
A back panel 24 is foldably connected to the rear edge of the bottom wall which folded, in assembly, is brought upwardly to a position that is perpendicular with the bottom panel to form the rear wall for the housing. A rear closure panel 25 is foldably attached to the back edge of the top panel 23 which is folded downwardly in assembly. The closure panel contains a rectangular shaped tongue 27 that is slidably received in a slotted hole 28 formed in back panel 24. As best seen in FIG. 3, the two rear panels interlock in assembly to totally enclose the back of the housing to provide added protection for material placed in the housing and also provide added structural strength to the assembly. An opening 30 is provided in the front of the housing through which material is passed therein.
The support standard section 12 of the present invention involves three cojoined panels that are foldably connected to the side edge 31 of top panel 23. These panels include a main support panel 33, a bladed front panel 34 and a locking panel 35.
The main support panel 33 contains two parallel side edges 37 and 38 which are normal to the side edge 31 of the top panel as illustrated in FIG. 2. The width of the support panel is about half the length of the top panel to which it is appended. The rear side edge 38 of the support panel is cut in the blank so that it is coplanar with the back edge of the top panel. As illustrated in FIG. 1, the support panel, when folded in assembly, depends downwardly from the top panel and is held in overlying contact against right side panel 21 of the housing.
The bladed front panel 34 of the support standard section is foldably connected to the main support panel along edge 37. The width of the bladed panel is substantially equal to the width of the bottom panel 20 of the housing section. The blank is cut so that the top edge 40 of the bladed section is parallel with the side edge 31 of the housing section top panel 23 prior to folding. The distance between edges 40 and 31, as shown in FIG. 2, is substantially equal to the width of the housing side panels 21 and 22. The bladed panel, in assembly, is folded under the housing at a right angle to the support panel as shown in FIG. 1 to position it directly below the midsection of the housing. The blank is accurately cut so that the edge 40 of the bladed panel will fit snuggly against the bottom surface of the housing to provide added support to the housing in assembly.
The lower or distal end of the bladed panel 34 is brought to a relatively sharp point by means of two oblique edges 43 and 44 that are arranged to meet and form an apex at the longitudinal axis 45 of the panel. The blade-like configuration of panel 34 permits the temporary receptacle to be easily inserted to a sufficient depth in a bank of snow to firmly anchor the device in place as shown in FIG. 3. The standard may also be placed against an existing post, such as post 13, and secured thereto using a staple gun or the like.
The entire assembly is locked in place by means of a locking panel 35 that contains a locking tab 47 extending outwardly from the top edge of the panel. The locking tab is undercut slightly at the point where it joins panel 35 by means of a pair of notches 48--48 which permits the tab to be bent along the line of joinder with the panel without unduly weakening the structure. In assembly, the locking panel is turned rearwardly 90° from the bladed panel and the locking tab is inserted into a slotted hole 50 formed in the bottom panel 20 of the housing section. Once the tab is locked in place, the entire assembly will be prevented from moving or otherwise shifting out of the desired position.
The lower edges 51 and 52 of support panel 33 and locking panel 35, respectively, are inclined upwardly away from the bladed panel as shown in FIG. 2. The upward inclination of the two edges presents a sloping edge to the snow when the standard is inserted into a snowbank thereby making insertion of the device relatively easy to achieve.
While this invention has been described with reference to the structure disclosed herein, it is not confined to the details set forth and this application is intended to cover any modifications or changes as may come within the scope of the following claims. | A temporary material receptacle that is suitable for use in snowbound regions in which delivery boxes are oftentimes buried under deep drifts or torn away by snow plowing equipment. The receptacle is formed by folding a single blank of suitable material into a rectangular shaped open ended housing that is supported in a generally horizontal position by a vertical standard. The standard can be easily inserted into a snowbank to provide for a temporary depository that is capable of shielding material contained therein from the elements. Alternatively, the standard can be secured as by stapling to an existing post or pole. | 0 |
CROSS REFERENCE TO RELATED APPLICATION
This application is a divisional application and claims priority to U.S. patent application Ser. No. 13/342,104 filed on Jan. 1, 2012. Pending application is hereby incorporated by reference in their entireties for all their teachings.
FIELD OF TECHNOLOGY
This disclosure generally relates to synthesize zinc oxide nanoparticles in either water or ethanol (EtOH) at room temperature (RT); and using the said nanoparticles for photo-catalytically degrading cyanide present in soil or water as toxic contaminant.
BACKGROUND
Cyanide is used or produced in several industries such as gas production, metal plating, pharmaceuticals, and mining [Botz et al. 2004, Young C. A. 2001]. This extensive use of cyanide has resulted in the generation of billions of cyanide waste gallons, which has increased the cyanide spill risk to the environment at several locations such as those at Baia Mare (Romania), Kumtor (Kyrgyzstan), Omai (Guyana), and Summitville (Colo.) [Deschenes et al. 2004, Chew et al. 1999]. Thus, cyanide must be treated before discharging.
Various treatment procedures such as adsorption, complexation, and oxidation are known for treating cyanides [Botz et al. 2004, Young C. A. 2001, Young et al 2001, Otto et al. 1980, Gurol et al. 1985]. The procedures other than oxidation give highly concentrated products in which toxic cyanides still exist. The most common method for treating cyanide is alkaline chlorination. However, improper chlorination of cyanide leads to evolution of toxic cyanogen chloride (NCCl). Chlorination also gives high total dissolved solids (TDS) in the treated water. However, ferrate [FeO 4 ] 2− , as a green chemical oxidant, can address some of the concerns of chlorination in the treatment of cyanides [Chang et al. 1997, O'Brien et al. 1998].
There is a need to remove the cyanide, as pollutant, so that existing limited water resources may be purified and recycled. There is also a serious need to clean up the soil from cyanide. There is a need for establishing an inexpensive and efficient method for removing cyanide.
SUMMARY
The invention discloses a novel method for synthesizing ZnO nanoparticles photo-catalyst and the effect of synthesizing medium on their physico-chemical properties. The instant disclosure also discloses a process of using the ZnO nanoparticles to remove cyanide from water and soil by photo-catalysis method.
In one embodiment, method of synthesizing ZnO nanoparticles at RT from zinc nitrate hexahydrate and cyclohexylamine (CHA) in aqueous solution is described.
In one embodiment, the morphology of zinc oxide nanoparticles prepared in water (ZnO W ) is determined by the physiochemical properties of the synthesis medium. In another embodiment, ZnO W IS used in different weight ratios to perform the photo-catalytic degradation of cyanide present in aqueous solution.
In another embodiment, characterizations of several properties of the novel ZnO W nanoparticles were performed. These characterizations were performed to prove the purity and efficacy of the prepared ZnO materials as well as to demonstrate the current methods efficiency and effectiveness.
In one embodiment, kinetics for cyanide photo-catalytic degradation was investigated with respect to ZnO W weight loading percentage.
In one embodiment, a well-controlled synthesis process at RT for economical use of ZnO in catalytic applications such as water treatment and other environmental applications are disclosed. In another embodiment, a direct, simple, room-temperature synthesis method for ZnO nanoparticles using CHA, as a precipitating agent, and zinc nitrate hexahydrate, as a source of zinc, in either aqueous or EtOHic media are disclosed.
The novel method of synthesizing ZnO W nanoparticles and method of using them in the photo-catalytic degradation of cyanide in aqueous solutions, disclosed herein, may be implemented in any means for achieving various aspects. Other features will be apparent from the accompanying figures and from the detailed description that follows.
BRIEF DESCRIPTION OF THE DRAWINGS
Example embodiments are illustrated by way of example and no limitation in the tables and in the accompanying figures, like references indicate similar elements and in which:
FIG. 1 shows diffuse reflectance infrared fourier transform (DRIFT) spectra of ZnO nanoparticles, prepared in either H 2 O, before calcination.
FIG. 2 shows X-ray diffraction (XRD) patterns of uncalcined ZnO nanoparticles, prepared in EtOH (A) and H 2 O (B). XRD patterns of calcined ZnO nanoparticles at 500° C., prepared in H 2 O(C) and EtOH (D).
FIG. 3 shows the survey spectra of X-ray photoelectron spectroscopy (XPS) for ZnO.⅓H 2 O, obtained in EtOH medium (A), Zn 2 3/2 XP spectra of ZnO.⅓H 2 O (B) and O 1 s XP spectra of ZnO.⅓H 2 O(C).
FIG. 4 shows the survey spectra of XPS for ZnO.½H 2 O (A), obtained in H 2 O medium, Zn 2p 3/2 XP spectra of ZnO.½H 2 O (B) and O 1 s XP spectra of ZnO.½H 2 O(C).
FIG. 5 (A) shows scanning electron micscpoicy SEM and (B) shows EDAX analysis for ZnO E before calcination.
FIG. 6 shows scanning electron microscope (SEM) (A) and Energy-dispersive X-ray spectroscopy (EDX) analysis of ZnO E after calcination (B).
FIG. 7 shows SEM (A) and EDX (B) analysis of ZnO W before calcination.
FIG. 8 shows SEM (A) and EDX (B) analyses of ZnO W after calcination.
FIG. 9 shows TEM images of calcined ZnO E nanoparticles (×200 k) (A) and ZnO W (×300 k)(B).
FIG. 10 shows UV-Vis absorption spectrum (A) and direct band-gap (B) for ZnO E .
FIG. 11 shows UV-Vis absorption spectrum (A) and direct band-gap (B) for ZnO W .
FIG. 12 shows Photodegradation kinetic of cyanide ion over calcined ZnO E .
Other features of the present embodiments will be apparent from the accompanying figures, tables and from the detailed description that follows.
DETAILED DESCRIPTION
Several embodiments for novel synthesizing method for ZnO W nano particles and their application in the photo-catalytic degradation of cyanide in water and soil are disclosed. Although the present embodiments have been described with reference to specific example embodiments, it will be evident that various modifications and changes may be made to these embodiments without departing from the broader spirit and scope of the various embodiments.
Synthesis of ZnO W Nanoparticles:
Materials-Zinc nitrate hexahydrate (pure, POCH), cyclohexylamine (GC>99%, Merck), absolute EtOH (99.9%, Scharlau), potassium cyanide (≧97%, Sigma-Aldrich), potassium iodide (≧99.5%, Sigma-Aldrich), and ammonia solution (28-30% NH 3 basis, Sigma-Aldrich) were commercially available and were used as received. Deionized water (18.2 MΩ·cm) was obtained from a Milli-Q water purification system (Millipore).
Method of Synthesizing and Characterization of the ZnO W Nanoparticles:
Preparation of ZnO Nanoparticles in Water (ZnO W )
A 30 mmol of zinc nitrate hexahydrate was dissolved in 60 ml of water at RT under stirring. In a separate beaker, 60 mmol of CHA was dissolved in 20 ml water at RT. The CHA solution was poured into the zinc solution, resulting in a white precipitate, upon stifling. An extra amount of 80 ml water was added to the reaction mixture, which left stifling for four days. The precipitate was filtered through F-size fritted filter, and then was washed with 100 ml water. The precipitate was dried under vacuum for one day. After drying, the precipitate was mixed with 300 ml water and was magnetically stirred for one day for removing impurity. The precipitate was filtered and was dried to give 2.432 g (yield %=89.68) of ZnO.½H 2 O, as proven by ICP elemental analysis [Zn (cal. 72.34%, exp. 72.88%].
Characterization of Materials and Nanoparticles:
ICP was used to determine the content of zinc component in the unclacined ZnO, obtained at RT.
XRD patterns were recorded for phase analysis and crystallite size measurement on a Philips X pert pro diffractometer, operated at 40 mA and 40 kV by using CuK α radiation and a nickel filter, in the 2 theta range from 2 to 80° in steps of 0.02°, with a sampling time of one second per step. The crystallite size was estimated using Scherer's equation. XRD patterns were recorded for ZnO materials before calcination and after calcination at 500° C. XPS spectra for uncalcined ZnO powder samples were recorded on Jeol JPS 9010MC spectrometer by using MgK α X-ray radiation (hv=1253.6 eV), operated at 20 mA and 10 kV. The base pressure in the analysis chamber was kept around 2.6×10 −7 Pa. Energy scales were referred to the line of Al 2p at 73.9 eV.
DRIFT spectra of ground, uncalcined ZnO powder samples, diluted with IR-grade potassium bromide (KBr), were recorded on a Perkin Elmer FTIR system spectrum GX in the range of 400-4000 cm −1 at room temperature.
Solid-state ultraviolet-visible (UV-Vis) absorption spectra for calcined ZnO powder samples were recorded on a Perkin Elmer Lambda 950 UV/Vis/NIR spectrophotometer, equipped with 150 mm snap-in integrating sphere for capturing diffuse and specular reflectance.
The morphology was investigated using a field-emission scanning electron microscope (FE-SEM model: FEI-200NNL), equipped with energy dispersive X-ray (EDX) spectrometer for elemental analysis, and a high-resolution transmission electron microscope (HRTEM model: JEM-2100F JEOL). EDX spectrometry was used to analyze the surface chemical composition of the ZnO samples. Carbon-coated copper grids were used for mounting the samples for HRTEM analysis.
The photocatalytic evaluation was carried out using a horizontal cylinder annular batch reactor. A black light-blue florescent bulb (F18W-BLB) was positioned at the axis of the reactor to supply UV illumination. The reaction suspension was irradiated by UV light of 365 nm at power of 18 W. The experiments were performed by suspending 0.0083, 0.0166, 0.0333, 0.0500, or 0.0666 wt. % of calcined ZnO into a 300-ml, 100 ppm potassium cyanide (KCN) solution, with its pH adjusted to 8.5 by ammonia solution. The reaction was carried out isothermally at 25° C. and samples of the reaction mixture were taken at different intervals over a total reaction time of six hours. The CN − (aq) concentration in the samples was estimated by volumetric titration with AgNO 3 , using potassium iodide to determine the titration end-point. The removal efficiency of CN − (aq) has been measured by applying the following equation; % Removal efficiency=(C o −C)/C o ×100 where C o is the initial concentration of CN − (aq) and C is the concentration of uncomplexed CN − (aq) in solution.
Results and Discussion
Formation of zinc oxide from the combination of zinc nitrate hexahydrate and CHA in aqueous medium can be illustrated by equation (1):
Zn(NO 3 ) 2(aq or alc) +2C 6 H 11 NH 2(aq or alc) +H 2 O→ZnO( nc )+2C 6 H 11 NH 3 (Eq. 1)
CHA, according to equation 1, acts as a base in the Brønsted-Lowry sense, but not as a base in the Lewis sense (a ligand). This behavior of CHA was proven by the isolation and determination of the structure of cyclohexylammonium nitrate crystals by single-crystal X-ray diffraction. This observed Brønsted-Lowry basicity of CHA can be attributed to its moderate base strength (pK b =3.36) when hydrolyzing in water according to equation 2:
C 6 H 11 NH 2(aq) +H 2 O (1) ⇄C 6 H 11 NH 3 + (aq) +OH − (aq) (Eq. 2)
Due to the high basicity of the CHA solution (pH=12.5), zinc ions react with the hydroxide ions and form different hydroxyl complexes such as [ZnOH] + , [Zn(OH) 2 ] (aq) , [Zn(OH) 3 ] + (aq) , and [Zn(OH) 4 ] 2− (aq) . Furthermore, the high basicity makes the chemical potential of hydroxide ion [OH − ] high, leading to a shift in the equilibrium in equation 3 towards the formation of oxide ion (O 2− ):
2OH − (aq) ⇄O 2− (aq) +H 2 O (1) (Eq. 3)
The formation of zinc hydroxide complexes and oxide ions shifts the equilibrium in equation 2 forward, causing further protonation of CHA and the formation of more hydroxide ions.
The formation of oxide ion according to equation 3 is responsible for the construction of Zn—O—Zn bonds by transforming the zinc hydroxide complexes into solid-phase according to equation 4:
2[Zn(OH) n ] 2-n (aq) ⇄[Zn 2 O(OH) 2n-2 ] 4-2n (aq) +H 2 O (1) (Eq. 4)
Equation 4 shows that the construction of ZnO crystal takes place via the interaction between the surface hydroxide of the growing crystals and the hydroxide ligands of the zinc complexes. Therefore, the formation of ZnO, according to the above proposed mechanism, is due to the high basicity of the reaction medium, which causes an increase in the concentration of the precursors (zinc hydroxide complexes) and an increase in the chemical potential of hydroxide ions.
FIG. 1 shows the DRIFT spectra of the uncalcined ZnO nanoparticles, prepared in H 2 O media. The absorption bands in the region of 600-400 cm −1 can be attributed to the crystal or lattice water. In addition, the asymmetric and symmetric stretching H—O—H vibration bands are observed between 3600 and 3200 cm −1 while the bending H—O—H vibration bands are observed between 1630 and 1600 cm −1 . The water diagnosis by DRIFT is in agreement with the ICP prediction of water presence in the uncalcined ZnO W and ZnO E as shown above (see para 0029 and 0030).
FIGS. 2A , 2 B, 2 C, and 2 D show the XRD diffraction patterns of all investigated solids. The patterns consist of broad peaks, which match the common ZnO hexagonal phase, i.e wurtzite structure. Before calcination, the sharper, higher peak intensities of ZnO W than those of ZnO E implies that the latter has a smaller crystallite size than that of the former. The average crystallite size, estimated by Scherrer's equation for the (100), (002) and (101) diffractions peaks, for ZnO E is almost half that of ZnO W (Table 1). After calcination, however, both of ZnO E and ZnO W had the same average crystallite size of 28.83 nm (Table 1). Such observation could be contributed to the difference in the number of moles of water of crystallization in each material, resulting in more shrinkage relative to particle coarsening the effect upon calcination for the ZnO W .
TABLE 1
Average crystallite size of ZnO E and ZnO W before and after calcinations.
Average
Miller Indices (hkl)
crystallite
100
002
101
size (nm)
Crystallite
Before
ZnO E
13.95
14.47
18.24
15.55
size (nm)
Calcination
ZnO W
33.49
28.96
39.25
33.90
After
ZnO E
33.45
24.83
28.22
28.83
Calcination
ZnO W
33.45
24.83
28.22
28.83
FIG. 3 shows a typical wide scan spectrum for the uncalcined ZnO E . The photoelectron peaks of Zn and O arise from the nanoparticles while C 1 s peak detection is attributed to the carbon paste, used to stick the sample on the mount. The chemical state of Zn in ZnO E nanoparticles is analyzed in detail by investigating Zn 2p 3/2 , Auger Zn LMM and O 1 s peaks. A noticeable shift was observed in the Auger signal spectra because of their high sensitivity to the chemical environment. The shown Zn 2p 3/2 photoelectron line at BE of 1021.3 eV is characterizing the ZnO state. The asymmetric O 1 s peak was coherently fitted by two nearly Gaussian components, centered at 531.4 eV and 529.9 eV, characterizing the ZnO states. The same features were observed for the ZnO W nanoparticles, as shown in FIG. 4 . The Zn 2p 3/2 line at BE of 1026 eV, indicates the existence of ZnO state. The O 1 s line shows two nearly Gaussian components, centered at 529.8 and 531.3 eV, indicating the presence of ZnO state.
FIGS. 5A and 6A show the SEM images of ZnO E before and after calcination, respectively, while FIGS. 7A and 8A show the SEM images of ZnO W before and after calcination, respectively. ZnO E , before calcination, is composed of homogeneously defined nanoparticles. On the other hand, ZnO W , before calcination, is made of irregularly-shaped, overlapped nanoparticles. Removal of lattice water upon the calcination process enhanced the nanoparticles features. Regular, polyhedral nanoparticles of an average size of 21 nm were observed for ZnO E after calcination. In homogenous, spherical particles with an average particle size of 32 nm along with some chunky particles were observed for ZnO W . The EDX analyses before and after calcination ( FIGS. 5B , 6 B, 7 B, and 8 B) indicate the purity of all the synthesized samples with no peaks other than Zn and O. The Au peak is due to the conductive coating layer of gold. The EDX results are in parallel with the XP spectra, where both analyses proved the purity of the prepared zinc oxide.
TEM images ( FIG. 9 ) of the samples after calcination supported the SEM micrographs regarding the morphology of ZnO nanoparticles. ZnO E nanoparticles adopt hexagonal shape ( FIG. 9A ), which is consistent with the regular, polyhedral morphology observed by SEM ( FIG. 6A ). However, ZnO W nanoparticles adopt an irregular spherical shape ( FIG. 9B ), which is consistent with the observed morphology by SEM ( FIG. 8A ). The more uniform polyhedral particles of ZnO E could be attributed to the lower polarity of EtOH, compared to that of water, leading to slower ionization and deposition rate and inhomogeneous nucleation that favor the polyhedral-shaped particles.
FIGS. 10A and 11A exhibit the UV-Vis absorption spectra for ZnO E and ZnO W , respectively. The direct band-gap (E g ) estimations from these spectra for ZnO E and ZnO W are depicted in FIGS. 10B and 11B , respectively, where the x-axis is the photon energy (E) in eV and y-axis is the square of the product of absorbance (A) and energy (AE) 2 . The absorption spectra and the E g (3.16 eV) for both materials are identical. Such observation implies that the optical properties of these materials are independent of their morphology (shape and size), and hence, are not affected by the synthesis medium.
Photocatalytic Degradation of Cyanide
Effect of the synthesis medium on photo-catalytic oxidation: The mechanism for the photocatalytic oxidation of cyanide by zinc oxide can be illustrated as follows:
ZnO+2 hv =ZnO(2 h + +2 e − )
½O 2 +2 e − +H 2 O=2OH −
2OH − +2 h + =2OH.
CN − +2OH.=OCN − +H 2 O
2OCN − +O 2 =2CO 2 +N 2
The overall reaction:
ZnO/H 2 O2CN − +2O 2 →2CO 2 +N 2
UV-Light
where h is Planck's constant and ν is the frequency of UV light.
The effect of the synthesis medium on the photocatalytic efficiency of ZnO nanoparticles was explicitly noticed by the much higher efficiency of ZnO E than that of ZnO W in the photocatalytic degradation of cyanide ion in the aqueous medium under the same conditions.
Table 2 shows that the photocatalytic activity of ZnO E is ˜1.5 that of ZnO W when applying 0.0166 wt % of the ZnO photocatalyst. The higher performance of ZnO E can be attributed to the higher adsorption capability of its particles, owing to its regular, polyhedral surface faces.
TABLE 2
Effect of the synthesis medium
on photocatalytic activity.
Sample
% of cyanide degradation
ZnO E
86
ZnO W
56
Zinc oxide nanoparticles were readily prepared at RT from zinc nitrate hexahydrate and cyclohexylamine either in aqueous or EtOH medium. The calcined ZnO E had a regular, polyhedra morphology while the calcined ZnO W had an irregular spherical morphology, mixed with some chunky particles. The morphology was a key factor in the superior photocatalytic behavior of ZnO E over that of ZnO W . The differences in morphology and photocatalytic behavior are strongly influenced by the physicochemical properties of the synthesis medium. ZnO E and ZnO W both may be used for removing cyanide from aqueous solutions.
This shows an efficient removal of cyanide from aqueous solutions. Water and soil may be treated with nanoparticles of ZnO W to remove cyanide as contaminant by photocatalytic degradation. In addition, the specification and drawings are to be regarded in an illustrative rather than as in a restrictive sense. | A simple, room-temperature method of producing zinc oxide nanoparticles was established by reacting zinc nitrate hexahydrate and cyclohexylamine (CHA) in either aqueous or ethanolic medium. Particles of polyhedra morphology were obtained for zinc oxide, prepared in EtOH (ZnO E ) and zinc oxide prepared in water (ZnO W ). The results indicate that there are significant morphological differences between ZnO E and ZnO W . ZnO E showed a regular polyhedral shape, while spherical and chunky particles were observed for ZnO W . The morphology was crucial in enhancing the cyanide ion photocatalytic degradation efficiency of ZnO E by a factor of 1.5 in comparison to the efficiency of ZnO W at equivalent loading of 0.0166 ZnO nanoparticles wt %. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a novel hydroquinone derivative useful for treating various allergic diseases and a pharmaceutical use thereof. More particularly, the present invention relates to a therapeutic agent for allergic diseases which contains the hydroquinone derivative as an active ingredient.
2. Description of the Prior Art
Allergic reactions which cause allergic diseases are generally classified into types I to IV. Particularly, the type IV reaction has been known to be dominant in atopic dermatitis, contact dermatitis, chronic bronchial asthma, psoriasis, graft-versus-host diseases, and so on. Effectiveness of antihistaminics and chemical mediator release inhibitors against these diseases is limited, and therefore steroids have been used for their therapy. In addition, cyclosporin and taclorims have also been known to be effective for suppression of graft rejection and therapy for graft-versus-host diseases developed after transplantation, and their application has been expanded into therapy for dermatitis Lancet, 339, 1120 (1992); J. Invest. Dermatol, 98, 851 (1992), etc.!. However, such drugs are sometimes disadvantageous. Steroids cause undesirable side effects such as infectious diseases, atrophy of adrenal glands, osteoporosis, diabetes mellitus, and growth inhibition in children. For cyclosporin or taclorims, side effects caused by their immunosuppression effect, such as infectious diseases and diabetes mellitus, would be feared.
The applicant have proposed uracil derivatives which can inhibit type IV allergic reactions (see Japanese Patent Application Laid-open No.8-109171 which corresponds to EP700908A1). However, development of more potent and safe drugs for treating allergic diseases, especially those responsible for type IV allergic reactions, is still required.
OBJECTS AND SUMMARY OF THE INVENTION
In these situations, the present invention is intended to solve the above mentioned problems. Therefore, the object of the present invention is to provide a novel compound and a therapeutic agent comprising the compound as an active ingredient which are useful for treating various allergic diseases, especially those responsible for type IV allergic reactions.
The inventors have made intensive and extensive studies with a view toward developing a therapeutic agent which is effective for treating various allergic diseases, especially those responsible for type IV allergic reactions. As a result, it has been found that a hydroquinone derivative having a 2,4 (1H, 3H)-pyrimidinedione ring therein markedly inhibits type IV allergic reactions. The present invention is completed.
Accordingly, the object of the present invention is to provide a hydroquinone derivative of formula (I) below or a pharmaceutically acceptable salt thereof and a pharmaceutical composition containing the hydroquinone derivative or pharmaceutically acceptable salt thereof as an active ingredient, especially for treatment of allergic diseases: ##STR2## wherein:
R 1 is a phenyl group which is unsubstituted or substituted with a substituent or substituents each independently selected from the group consisting of a halogen atom, a C1-4 alkyl group and a C1-4 alkoxy group;
R 2 is a hydrogen atom or a C1-4 alkyl group;
each of R 3 and R 4 is independently a hydrogen atom or a C1-4 alkyl group;
R 5 is a hydrogen atom or a C1-4 alkyl group;
each of R 6 , R 7 and R 8 is independently a hydrogen atom or a C1-4 alkyl group;
P is a hydroxyl group;
Q is a hydroxyl group, a C1-4 alkoxy group, a C1-18 acyloxy group or an oxo group;
P may form together with Q an ether bond;
R is a hydroxyl group, a C1-4 alkoxy group, a C1-18 acyloxy group or an oxo group, provided that when either of the Q and the R is an oxo group, the other is also an oxo group;
X is a single bond, an --NR 10 -- group or a --CH 2 --NR 10 -- group in which R 10 is a hydrogen atom or a C1-4 alkyl group;
Y is a methylene group or a carbonyl group; and
dotted bonds in a six membered ring represent that the six membered ring has the maximum number of double bonds.
The hydroquinone derivative and pharmaceutically acceptable salt thereof of the present invention are concretely explained as follows.
The hydroquinone derivative of the present invention has an asymmetric carbon atom attached by R 5 and P as shown in formula (I), which leads two types of enantiomers depending on the steric configuration of R 5 and P on the asymmetric carbon atom. In the present invention, both of the enantiomers are included.
The hydroquinone derivative of the present invention contains a hydroquinone-related moiety represented by formula (II): ##STR3## wherein P, Q, R, R 5 , R 6 , R 7 and R 8 are the same as defined for formula (I) above, and dotted bonds in a six membered ring represent that the six membered ring has the maximum number of double bonds.
The moiety of formula (II) has the following three types of variations depending on the P, Q, and R selected therein.
At first, when P forms together with Q an ether bond, the moiety of formula (II) has a chroman-type structure of formula (III): ##STR4## wherein R 5 , R 6 , R 7 and R 8 are the same as defined for formula (I) above; and R 12 is a hydrogen atom, a C1-4 alkyl group or a C1-18 acyl group.
At second, when P is a hydroxyl group and each of Q and R is independently a hydroxyl group, a C1-4 alkoxy group or a C1-18 acyloxy group, the moiety of formula (II) has a hydroquinone-type structure of formula (IV), which is a hydrated form of the above mentioned chroman-type structure (III): ##STR5## wherein R 5 , R 6 , R 7 and R 8 are the same as defined for formula (I); and each of R 11 and R 12 is independently a hydrogen atom, a C1-4 alkyl group or a C1-18 acyl group.
At last, when P is a hydroxyl group and both of Q and R are oxo groups, the moiety of formula (II) has a quinone-type structure of formula (V), which is an oxidized form of the above mentioned hydroquinone-type structure (IV): ##STR6## wherein R 5 , R 6 , R 7 and R 8 are the same as defined for formula (I) above.
In general, these three types of structures of the hydroquinone-related moiety closely relate to one another, and the interconversion between them is reversible see, e.g., J. Org. Chem., 46, 2445 (1981)!. For example, with respect to the interconversion between the chroman-type structure (III) and the quinone-type structure (V), it has been known that α-tocopherol containing the structure of formula (III) (wherein R 5 =R 6 =R 7 =R 8 =CH 3 , and R 12 =H) as a partial moiety produces in vivo α-tocopherol quinone which has the structure of formula (V) therein as a partial moiety see, e.g., J. Biol. Chem., 238, 2912 (1963)!.
In formula (I), each of R 2 , R 3 , R 4 R 5 , R 6 , R 7 , R 8 and R 10 is a hydrogen atom or a C1-4 alkyl group such as methyl group, ethyl group, propylgroup, isopropyl group, butyl group, sec-butyl group, tert-butyl group and isobutyl group. Particularly preferred is a hydrogen atom or methyl group.
As the hydroquinone-related moiety of formula (II), which is a partial structure of the compound of formula (I) of the present invention, preferred are those in which each of R 5 , R 6 , R 7 and R 8 is a hydrogen atom or a methyl group. Specific examples of such moiety of formula (II) include: for the chroman-type structure of formula (III), 2-methyl-6-hydroxy-2-chromanyl group, 2,8-dimethyl-6-hydroxy-2-chromanyl group, 2,5,8-trimethyl-6-hydroxy-2-chromanyl group, 2,7,8-trimethyl-6-hydroxy-2-chromanyl group and 2,5,7,8-tetramethyl-6-hydroxy-2-chromanyl group; for the hydroquinone-type structure of formula (IV), 3-(2,5-dihydroxyphenyl) -1-hydroxy-1-metylpropyl group, 3-(2,5-dihydroxy-3-methylphenyl)-l-hydroxy-l-metylpropyl group, 3-(2,5-dihydroxy-3,6-dimethylphenyl)-1-hydroxy-1-metylpropyl group, 3-(2,5-dihydroxy-3,4-dimethylphenyl)-1-hydroxy-1-metylpropyl and 3-(2,5-dihydroxy-3,4,6-hydroxy-1-metylpropyl group; and for the quinone-type structure of formula (V), 3-(1,4-benzoquinon-2-yl)-1-hydroxy-1-metylpropyl group, 1-hydroxy-1-methyl-3-(6-methyl-1,4-benzoquinon-2-yl)propyl group, 3-(3,6-dimethyl-1,4-benzoquinon-2-yl)-1-hydroxy-1-metylpropyl group, 3-(5,6-dimethyl-1,4-benzoquinon- 2-yl)-1-hydroxy-1-metylpropyl group and 1-hydroxy-l-methyl -3-(3,5,6-trimethyl-1, 4-benzoquinon-2-yl)propyl group. Among them, especially preferred are 2,5,7,8-tetramethyl-6-hydroxy-2-chromanyl group, 3-(2,5-dihydroxy-3,4,6-trimethylphenyl)-1-hydroxy-1-methylpropyl group and 1-hydroxy-1-methyl-3-(3,5,6-trimethyl-1,4-benzoquinon-2-yl)propyl group.
A hydrogen atom of a phenolic hydroxyl group in a benzene ring of the chroman-type structure of formula (III) or the hydroquinone-type structure of formula (IV) may be replaced by a C1-4 alkyl group or a C1-18 acyl group. That is, in formula (III), R 12 is a hydrogen atom, a C1-4 alkyl group or a C1-18 acyl group, and more preferably a hydrogen atomor aC1-18 acyl group. In formula (IV), each of R 11 and R 12 is independently a hydrogen atom, a C1-4 alkyl group or a C1-18 acyl group, and more preferably a hydrogen atom or a C1-18 acyl group. When each of R 11 and R 12 is a hydrogen atom or an acyl groups, corresponding each of OR 11 and OR 12 becomes a hydroxyl group or a hydroxyl group protected with an acyl group. Specific examples of such acyl group include an alkanoyl group such as a formyl group, an acetyl group, a propionyl group, a butyryl group, a pentanoyl group, a hexanoyl group, an octanoyl group, a decanoyl group, a dodecanoyl group, a tetradecanoyl group, a hexadecanoyl group and an octadecanoyl group; and an acyl group containing an aromatic ring such as a benzoyl group, an anisoyl group (methoxybenzoyl group), a phenylacetyl group and a phenylpropionyl group.
In formula (I), R 1 at the 1-position of 2,4 (1H, 3H) -pyrimidinedione ring is a phenyl group unsubstituted or substituted with a substituent or substituents each independently selected from the group consisting of a halogen atom, a C1-4 alkyl group and a C1-4 alkoxy group. The halogen atom used herein is fluorine, chlorine, bromine or iodine, and preferably fluorine, chlorine or bromine. The C1-4 alkyl group is alinearor branchedalkyl group, such as a methyl group, an ethyl group, a propyl group, an isopropyl group, a butyl group, a sec-butyl group, a tert-butyl group or an isobutyl group. The C1-4 alkoxy group is an alkyl-oxy group comprising the alkyl group. The substituted phenyl group of R 1 is exemplified as follows.
Specific examples of the phenyl group substituted with a halogen atom or halogen atoms (e.g., fluorine, chlorine and bromine) include 2-fluorophenyl, 3-fluorophenyl, 4-fluorophenyl, 2-chlorophenyl, 3-chlorophenyl, 4-chlorophenyl, 2-bromophenyl, 3-bromophenyl, 4-bromophenyl, 2,3-difluorophenyl, 2,4-difluorophenyl, 2,5-difluorophenyl, 2,6-difluorophenyl, 3,4-difluorophenyl, 3,5-difluorophenyl, 2,3-dichlorophenyl, 2,4-dichlorophenyl, 2,5-dichlorophenyl, 2,6-dichlorophenyl, 3,4-dichlorophenyl, 3,5-dichlorophenyl, 2,4-dibromophenyl, 2,5-dibromophenyl, 2,6-dibromophenyl, 2-chloro-4-fluorophenyl, 3-chloro-4-fluorophenyl, 4-chloro-2-fluorophenyl, 4-bromo-2-chlorophenyl, 2,3,4-trifluorophenyl, 2,3,6-trifluorophenyl, 2,4,5-trifluorophenyl, 2,4,6-trifluorophenyl, 2,3,4-trichlorophenyl, 2,4,5-trichlorophenyl, 2,4,6-trichlorophenyl, and 3,4,5-trichlorophenyl groups. Specific examples of the phenyl group substituted with a C1-4 alkyl group or C1-4 alkyl groups include 2-methylphenyl, 3-methylphenyl, 4-methylphenyl, 2-ethylphenyl, 3-ethylphenyl, 4-ethylphenyl, 2-propylphenyl, 4-propylphenyl, 2-tert-butylphenyl, 4-butylphenyl, 4-tert-butylphenyl, 4-sec-butylphenyl, 2,3-dimethylphenyl, 2,4-dimethylphenyl, 2,5-dimethylphenyl, 2,6-dimethylphenyl, 3,4-dimethylphenyl, 3,5-dimethylphenyl, 2,6-diethylphenyl, 2,5-di-tert-butylphenyl, 3,5-di-tert-butylphenyl and 2,4,6-trimethylphenyl groups.
Specific examples of the phenyl group substituted with a C1-4 alkoxy group or C1-4 alkoxy groups include 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-ethoxyphenyl, 3-ethoxyphenyl, or 4-ethoxyphenyl group.
The phenyl group of R 1 in formula (I) may be substituted with a plurality of deferent types of substituents. Specific examples of such substituted phenyl group include 2-fluoro-4-methylphenyl, 2-fluoro-5-methylphenyl, 3-fluoro-2-methylphenyl, 3-fluoro-4-methylphenyl, 4-fluoro-2-methylphenyl, 5-fluoro-2-methylphenyl, 2-chloro-4-methylphenyl, 2-chloro-5-methylphenyl, 2-chloro-6-methylphenyl, 3-chloro-2-methylphenyl, 3-chloro-4-methylphenyl, 2-bromo-4-methylphenyl, 3-bromo-4-methylphenyl, 4-bromo-2-methylphenyl, 4-bromo-3-methylphenyl, 3-fluoro-2-methoxyphenyl, 3-fluoro-4-methoxyphenyl, 3-chloro-4-methoxyphenyl, 5-chloro-2-methoxyphenyl, 2-chloro-5-methoxyphenyl, 2-methoxy-5-methylphenyl, 2-methoxy-6-methylphenyl, 4-methoxy-2-methylphenyl and 5-methoxy-2-methylphenyl groups.
In formula (I), R 2 at the 3-position of 2,4 (1H, 3H) -pyrimidinedione ring is a hydrogen atom or a C1-4 alkyl group, and preferably a hydrogen atom or a methyl group. Each of R 3 and R 4 in NR 3 R 4 at the 6-position of 2,4 (1H, 3H)-pyrimidinedione ring in formula (I) is also a hydrogen atom or a C1-4 alkyl group, and preferably a hydrogen atom or a methyl group.
In the compound of formula (I), one containing the chroman moiety of formula (III) has a basic structure in which a 2,4 (1H, 3H)-pyrimidinedione ring is connected to the chroman ring through a --X--Y--group. Examples of such basic structure include those in which X is an --NR 10 --group and Y is a carbonyl group, such as 5-(chroman-2-carboxamido)-2,4 (1H, 3H)-pyrimidinedione, 5-(N-ethylchroman-2-carboxamido)-2,4 (1H, 3H)-pyrimidinedione (N-ethylchroman-2-carboxamido)-2,4 (1H, 3H)-pyrimidinedione, 5-(N-propylchroman-2-carboxamido)-2,4 (1H, 3H)-pyrimidinedione and 5-(N-butylchroman-2-carboxamido)-2,4 (1H, 3H) -pyrimidinedione; those in which X is an -NR 10 - group and Y is a methylene group, such as 5- N- ( 2-chromanylmethyl)amino!-2,4 (1H, 3H)-pyrimidinedione, 5- N- ( 2-chromanylmethyl)-N-methylamino!-2,4 (lH, 3H)-pyrimidinedione, 5- N-(2-chromanylmethyl) -N-ethylamino!-2,4 (1H, 3H)-pyrimidinedione, 5- N-(2-chromanylmethyl)-N-propylamino!-2,4 (1H, 3H)-pyrimidinedione and 5- (N-butyl-N-(2-chromanylmethyl)amino!-2,4 (1H, 3H) -pyrimidinedione; those in which X is a single bond and Y is a methylene group or a carbonyl group, such as 5-(2-chromanylmethyl)-2,4 (1H, 3H)-pyrimidinedione and 5-(2-chromancarbonyl)-2,4 (1H, 3H)-pyrimidinedione; those in which X is --CH 2 --NR 10 --group and Y is a methylene group, such as 5- N-(2-chromanylmethyl)aminomethyl!-2,4 (lH, 3H)-pyrimidinedione, 5- N-(2-chromanylmethyl)-N-methylaminomethyl!-2,4 (1H, 3H) -pyrimidinedione, 5- N- ( 2-chromanylmethyl)-N-ethylaminomethyl) -2,4 (1H, 3H)-pyrimidinedione, 5- N-(2-chromanylmethyl) -N-propylaminomethyl!-2,4 (1H, 3H)-pyrimidinedione and 5- N-butyl-N-(2-chromanylmethyl)aminomethyl!-2,4 (1H, 3H) -pyrimidinedione; and those in which X is a --CH 2 --NR 10 --group and Y is a carbonyl group, such as 5-(chroman-2-carboxamidomethyl)-2,4 (1H, 3H)-pyrimidinedione, 5-(N-methylchroman-2-carboxamidomethyl)-2,4 (lH, 3H)-pyrimidinedione, 5-(N-ethylchroman-2-carboxamidomethyl)-2,4 (lH, 3H)-pyrimidinedione, 5-(N-propylchroman-2-carboxamidomethyl)-2,4 (1H, 3H) -pyrimidinedione and 5-(N-butylchroman-2-carboxamidomethyl)-2,4 (1H, 3H)-pyrimidinedione. These basic structures have the above mentioned R 1 , R 2 , and NR 3 R 4 at the 1-, 3- and 6-positions of the 2,4 (1H, 3H)-pyrimidinedione ring, respectively; and also have R 5 , R 6 , OR 12 , R 7 and R 8 at the 2-, 5-, 6-, 7- and 8-positions of the chroman ring, respectively.
In the compound of formula (I), one containing the hydroquinone moiety of formula (IV) has a basic structure having a 3-phenylpropyl group instead of the 2-chromanyl group in the above mentioned chroman ring-containing basic structure. The 3-phenylpropyl group has a hydroxyl group and R 5 at the 1-position of the propyl moiety thereof, and also has OR 1 , R 8 , R 7 , OR 12 and R 6 at the 2-, 3-, 4-, 5- and 6-positions of the phenyl moiety thereof, respectively.
In the compound of formula (I), one containing the quinone moiety of formula (V) has a basic structure having a 3-(t,4-benzoquinon-2-yl)propyl group instead of the 2-chromanyl group in the above mentioned chroman ring-containing basic structure. The 3-(1,4-benzoquinon-2-yl)propyl group has a hydroxyl group and R 5 at the 1-position of the propyl moiety thereof, and also has R 6 , R 7 , and R 8 at the 3-, 5- and 6-positions of the benzoquinone moiety thereof, respectively.
Proper selection of the substituents of the 2,4 (1H, 3H)-pyrimidinedione ring and the hydroquinone-related moiety of formula (II) can afford preferable hydroquinone derivative of the present invention. That is, selection of a hydrogen atom or a methyl group for R 2 , R 3 , and R 4 on the 2,4 (IH, 3H)-pyrimidinedione ring; R 5 , R 6 , R 7 , and R 8 on the moiety of formula (II); and R 10 in --X--Y--- affords the more preferable compound of formula (I). Selection of a methyl for all of R5, R 6 , R 7 , and R 8 affords the particularly more preferable compound of formula (I).
Specific examples of such particularly preferable hydroquinone derivative of formula (I) of the present invention include:
for those which have the chroman moiety of formula (III) therein,
6-amino-5-(6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxamido)-3-methyl-1-phenyl-2,4 (lH, 3H)-pyrimidinedione,
6-amino-i-(4-fluorophenyl)-5-(6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxamido)-3-methyl-2,4 (lH, 3H) -pyrimidinedione,
6-amino-i-(4-chlorophenyl)-5-(6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxamido)-3-methyl-2,4 (lH, 3H) -pyrimidinedione,
6-amino-i-(2-chlorophenyl)-5-(6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxamido)-3-methyl-2,4 (iH, 3H) -pyrimidinedione,
6-amino-i-(3-chlorophenyl)-5-(6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxamido)-3-methyl-2,4 (lH, 3H) -pyrimidinedione,
6-amino-5-(6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxamido)-3-methyl-i-(4-methylphenyl)-2,4 (1H, 3H) -pyrimidinedione,
6-amino-5-(6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxamido)-1-(4-methoxyphenyl)-3-methyl- 2 , 4 (1H, 3H) -pyrimidinedione,
5-(6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxamido)-3-methyl-6-methylamino-1-phenyl- 2 , 4(1H, 3H)-pyrimidinedione,
6-dimethylamino-l-(4-fluorophenyl)-5-(6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxamido)- 3 -methyl- 2 , 4 (1H, 3H) -pyrimidinedione,
5-(6-acetoxy-2,5,7,8-tetramethylchroman-2-carboxamido)-6-amino-3-methyl-1-phenyl-2,4 (1H, 3H)-pyrimidinedione,
6-amino-5- (6-hydroxy-2,5,7,8-tetramethyl- 2 -chromanylmethyl)amino!-3-methyl--phenyl- 2 , 4 (1H, 3H) -pyrimidinedione,
6-amino-5-(6-hydroxy-2,5,7,8-tetramethyl-2-chromanylmethyl)-3-methyl-l-phenyl-2,4 (1H, 3H)-pyrimidinedione,
6-amino-5-(6-hydroxy-2,5,7,8-tetramethyl-2-chromancarbonyl)-3-methyl-l-phenyl-2, 4 (1H, 3H)-pyrimidinedione,
6-amino-5- N-(6-hydroxy-2,5,7,8-tetramethyl-2-chromanylmethyl)aminomethyl!-3-methyl-1-phenyl-2,4 (1H, 3H) -pyrimidinedione,
6-amino-5-(6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxamidomethyl)-3-methyl-1-phenyl-2,4 (lH, 3H) -pyrimidinedione, and
6-amino-3-methyl-5-(N-methyl-6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxamidomethyl)-1-phenyl-2,4 (1H, 3H) -pyrimidinedione;
for those which have the hydroquinone moiety of formula (IV) therein,
6-amino-5- 4-(2,5-diacetoxy-3,4,6-trimethylphenyl)-2-hydroxy-2-methylbutyramidol!-3-methyl-1-phenyl-2,4(1h,3H)-pyrimidinedione,
6-amino-5- 4-(2,5-diacetoxy-3,4,6-trimethylphenyl)-2-hydroxy-2-methylbutyramido!-1-(4-fluorophenyl)-3-methyl,2,4(1H, 3H)-pyrimidinedione,
6-amino-l-(4-chlorophenyl)-5- 4-(2, 5-diacetoxy-3,4,6-trimethylphenyl)-2-hydroxy-2-methylbutyramido!-3-methyl-2,4 (lH, 3H)-pyrimidinedione,
6-amino-i-(2-chlorophenyl)-5- 4-(2,5-diacetoxy-3,4,6-trimethylphenyl)-2-hydroxy-2-methylbutyramido!-3-methyl-2,4 (1H, 3H)-pyrimidinedione,
6-amino-i-(3-chlorophenyl)-5- 4-(2,5-diacetoxy-3,4,6-trimethylphenyl)-2-hydroxy-2-methylbutyramido!-3-methyl- 2 , 4 (1H, 3H)-pyrimidinedione,
6-amino-5- 4-(2,5-diacetoxy-3,4,6-trimethylphenyl)-2-hydroxy-2-methylbutyramido!-3-methyl-1-(4-methylphenyl)-2,4 (1H, 3H) -pyrimidinedione,
6-amino-5- 4-(2,5-diacetoxy-3,4,6-trimethylphenyl)-2-hydroxy-2-methylbutyramido!-1-(4-methoxyphenyl)-3-methyl- 2 , 4 (1H, 3H)- pyrimidinedione,
5- 4-(2,5-diacetoxy-3,4,6-trimethylphenyl)-2-hydroxy-2-methylbutyramido!-3-methyl-6-methylamino-1-phenyl- 2 , 4 (1H, 3H)-pyrimidinedione,
5- 4-(2,5-diacetoxy-3,4,6-trimethylphenyl)-2-hydroxy-2-methylbutyramido!-6-dimethylamino-l-(4-fluorophenyl)-3-methyl-2,4 (1H, 3H)-pyrimidinedione,
6-amino-5-f4-(2,5-dihydroxy-3,4,6-trimethylphenyl)-2-hydroxy-2-methylbutyramido3-3-methyl-l-phenyl-2,4 (lH, 3H) -pyrimidinedione,
6-amino-5- 4-(2,5-diacetoxy-3,4,6-trimethylphenyl)-2-hydroxy-2-methylbutyl!amino!-3-methyl-i-phenyl-2,4 (1H, 3H) -pyrimidinedione,
6-amino-5- 4-(2,5-diacetoxy-3,4,6-trimethylphenyl)-2-hydroxy-2-methylbutyl!-3-methyl-1-phenyl-2,4 (lH, 3H)-pyrimidinedione,
6-amino-5- 4-(2,5-diacetoxy-3,4,6-trimethylphenyl)-2-hydroxy-2-methylbutyryl!-3-methyl-1-phenyl-2,4 (lH, 3H) -pyrimidinedione,
6-amino-5- N- 4-(2,5-diacetoxy-3,4,6-trimethylphenyl)-2-hydroxy-2-methylbutyl!aminomethyl!-3-methyl-l-phenyl-2,4 (1H, 3H)-pyrimidinedione, and
6-amino-5- 4-(2,5-diacetoxy-3,4,6-trimethylphenyl)-2-hydroxy-2-methylbutyramidomethyl!-3-methyl-1-phenyl-2,4 (1H, 3H) -pyrimidinedione;
for those which have the quinone moiety of formula (V) therein,
6-amino-3-methyl-l-phenyl-5- 4-(3,5,6-trimethyl-1,4-benzoquinon-2-yl)-2-hydroxy-2-methylbutyramido!-2,4 (lH, 3H) -pyrimidinedione,
6-amino-i-(4-fluorophenyl)-3-methyl-5- 4-(3,5,6-trimethyl-1,4-benzoquinon-2-yl)-2-hydroxy-2-methylbutyramido!-2,4 (lH, 3H) -pyrimidinedione,
6-amino-i-(4-chlorophenyl)-3-methyl-5- 4-(3,5,6-trimethyl-1,4-benzoquinon-2-yl)-2-hydroxy-2-methylbutyramido!-2,4 (lH, 3H) -pyrimidinedione,
6-amino-l-(2-chlorophenyl)-3-methyl-5- 4-(3,5,6-trimethyl-1,4-benzoquinon-2-yl)-2-hydroxy-2-methylbutyramido!-2,4 (1H, 3H) -pyrimidinedione,
6-amino-i-(3-chlorophenyl)-3-methyl-5-f4-(3,5,6-trimethyl-1,4-benzoquinon-2-yl)-2-hydroxy-2-methylbutyramido!-2,4 (lH, 3H) -pyrimidinedione,
6-amino-3-methyl-1-(4-methylphenyl)-5- 4-(3,5,6-trimethyl-1,4-benzoquinon-2-yl)-2-hydroxy-2-methylbutyramido!-2,4 (1H, 3H) -pyrimidinedione,
6-amino-i-(4-methoxyphenyl)-3-methyl-5- 4-(3,5,6-trimethyl-1,4-benzoquinon-2-yl)-2-hydroxy-2-methylbutyramido!-2,4 (1H, 3H)-pyrimidinedione,
3-methyl-6-methylamino-i-phenyl-5- 4-(3,5,6-trimethyl-1,4-benzoquinon-2-yl)-2-hydroxy-2-methylbutyramido!-2,4 (lH, 3H) -pyrimidinedione,
6-dimethylamino-1-(4-fluorophenyl)-3-methyl-5- 4-(3,5,6-trimethyl-1,4-benzoquinon-2-yl)-2-hydroxy-2-methylbutyramido!-2,4 (1H, 3H)-pyrimidinedione,
6-amino-3-methyl-l-phenyl-5- 4-(3,5,6-trimethyl-1,4-benzoquinon-2-yl)-2-hydroxy-2-methylbutyl!amino!-2,4 (lH, 3H) -pyrimidinedione,
6-amino-3-methyl-1-phenyl-5- 4-(3,5,6-trimethyl-1,4-benzoquinon-2-yl)-2-hydroxy-2-methylbutyl!-2,4 (1H, 3H) -pyrimidinedione,
6-amino-3-methyl-1-phenyl-5- N- 4-(3,5,6-trimethyl-1, 4-benzoquinon-2-yl)-2-hydroxy-2-methylbutyryl!aminomethyl!-2,4 (1H, 3H) -pyrimidinedione,
6-amino-3-methyl-i-phenyl-5- N- 4-(3,5,6-trimethyl-1,4-benzoquinon-2-yl)-2-hydroxy-2-methylbutyl!aminomethyl!-2,4 (1H, 3H) -pyrimidinedione,
6-amino-3-methyl-l-phenyl-5- 4-(3,5,6-trimethyl-1,4-benzoquinon-2-yl)-2-hydroxy-2-methylbutyramidomethyl!-2,4 (1H, 3H)-pyrimidinedione;
and pharmaceutically acceptable salts thereof. Here, the term "a pharmaceutically acceptable salt" means a sodium, potassium, calcium, ammonium, hydrochloride, sulfate, acetate or succinate salt of any of the hydroquinone derivatives which have a dissociating (i.e., salt-forming) functional group.
The hydroquinone derivative of formula (I) of the present invention can generally be prepared by synthesizing an intermediate corresponding to the 2,4 (1H, 3H)-pyrimidinedione moiety and an intermediate corresponding to the moiety of formula (II) separately and then coupling both of the intermediates to each other under an appropriate reaction condition. The intermediate corresponding to the 2,4 (lH, 3H)-pyrimidinedione moiety, 6-amino-2, 4 (lH, 3H) -pyrimidinedione, can be prepared, for example, by the method disclosed in Japanese Patent Application Laid-open No. 8-109171 (corresponding to EP 700908A1). With respect to the intermediate corresponding to the moiety of formula (II), an intermediate corresponding to the chroman-type structure of formula (III) can be synthesized, for example, by the method disclosed in USP 4026907; and an intermediate corresponding to the hydroquinone-type structure of formula (IV) or the quinone-type structure of formula (V) can be synthesized, for example, by the method described in J. Org. Chem., 46, 2445 (1981).
The hydroquinone derivative of formula (I) of the present invention may also be prepared in the following various ways depending on the types of the --X--Y--groups therein.
For example, a hydroquinone derivative of formula (I) in which --X--Y--is --NH--CO--may be prepared by introducing a nitroso or nitro group into a 6-amino-2,4 (1H, 3H)-pyrimidinedione derivative, reducing the resultant to obtain a 5,6-diamino-2,4 (1H, 3H)-pyrimidinedione derivative, and then condensing it with a carboxylic acid corresponding to any of formulae (III), (IV) and (V). The condensation process can be performed, for example, by a conventional method used for peptide synthesis such as a mixed anhydride method, an acid halide method, an activated ester method and a carbodiimide method.
A hydroquinone derivative of formula (I) in which --X--Y--is --NR 10 --CH 2 --may be prepared from a 5,6-diamino-2,4 (1H, 3H) -pyrimidinedione derivative and an aldehyde corresponding to formula (III), (IV) or (V) through reductive amination. It may also be prepared by reducing the above mentioned hydroquinone derivative of formula (I) in which --X--Y--is --NR 10 --CO---.
A hydroquinone derivative of formula (I) in which --X--Y--is --CH 2 --NR 10 --CO--may be prepared, for example, through Mannich aminomethylation of the 6-amino-2,4 (lH, 3H)-pyrimidinedione derivative into a 6-amino-5-(aminomethyl)-2,4 (lH, 3H) -pyrimidinedion6 derivative, followed by condensation with a carboxylic acid corresponding to formula (III), (IV) or (V). The 6-amino-5-(aminomethyl)-2,4 (1H, 3H)-pyrimidinedione derivative may also be prepared from the 6-amino-2, 4 (1H, 3H) -pyrimidinedione derivative through Sandmeyer formylation followed by reductive amination.
A hydroquinone derivative of formula (I) in which --X--Y--is --CH 2 --NR 10 --CH 2 --may be prepared, for example, from the 6-amino-5-aminomethyl-2,4 (1H, 3H)-pyrimidinedione derivative and an aldehyde corresponding to formula (III), (IV) or (V) through reductive amination thereof. It may also be prepared by reducing the above mentioned hydroquinone derivative of formula (I) in which --X--Y--is --CH 2 --NR 10 --CO--.
A hydroquinone derivative of formula (I) in which --X--Y--is --CH 2 --may be prepared from the 6-amino-2,4 (1H, 3H)- pyrimidinedione derivative and a chloromethyl derivative corresponding to formula (III), (IV) or (V).
A hydroquinone derivative of formula (I) in which --X--Y--is --CO-- may be prepared from the 6-amino-2,4 (1H, 3H) -pyrimidinedione derivative and a carboxylic acid corresponding to formula (III), (IV) or (V) through Friedel-Crafts acylation.
In the preparation of the hydroquinone derivative of formula (I) of the present invention, after the coupling of a 2,4 (1H, 3H)-pyrimidinedione moiety with a hydroquinone-related moiety of any of formulae (III), (IV) and (V), interconversion between the chroman-, hydroquinone- and quinone-type moieties in the resultant coupled compound may be performed.
Reaction conditions for the above mentioned process may be suitably selected depending on the types of the reaction or the reagents employed. In general, conditions commonly employed for those reactions can be used. If necessary, a process for introduction or elimination of protecting groups may additionally be employed.
The pharmaceutical composition of the present invention, which is concretely a therapeutic agent for allergic diseases, contains the above mentioned hydroquinone derivative of formula (I) or pharmaceutically acceptable salt thereof as an active ingredient. The pharmaceutical composition can be used in various forms, such as an external preparation (ointment, cream, etc.), an oral preparation (tablets, capsules, powder, etc.), inhalant, injection, and so on. For example, for the preparation of an ointment, the hydroquinone derivative or pharmaceutically acceptable salts thereof of the present invention may be mixed into an ointment base such as vaseline, and optionally additives such as an absorption accelerator may be added thereto. For the preparation of tablets, the hydroquinone derivative or pharmaceutically acceptable salt thereof of the present invention may be mixed with excipients (lactose and starch, etc.), lubricants (talk, magnesium stearate, etc.), and other additives.
Dose of the therapeutic agent for allergic diseases of the present invention should be suitably selected depending on sex, age, body weight, disease type and condition of the patient to be treated. For example, for a patient suffered from atopic dermatitis, contact dermatitis, psoriasis, or the like, anointment containing 0.01 to 10% of the active ingredient may be applied once or several times a day on the diseased portion of the patient. For a patient suffered from any of the above mentioned dermatitises, bronchial asthma, irritable pneumonia, graft rejection caused after transplantation, graft-versus-host diseases, or autoimmune diseases, for example, 0.01 to 100 mg/kg/day of dose in a male adult may be orally administered once a day or divided into several times a day as tablets, capsules or powder.
The hydroquinone derivative or a pharmaceutically acceptable salt thereof according to the present invention exhibits a markedly effective inhibitory action against allergic inflammations, especially those caused by type IV allergic reactions. Accordingly, the hydroquinone derivative or pharmaceutically acceptable salt thereof of the present invention is useful as a therapeutic agent for allergic diseases, especially those caused by type IV allergic reaction. In addition, it can be effectively absorbed through skin by percutaneous administration, and therefore is useful for treatment of various skin diseases such as atopic dermatitis, contact dermatitis and psoriasis. It can also be effectively absorbed through the digestive tract by oral administration, and therefore is useful for treatment of dermatitis covering a wide area, bronchial asthma, irritable pneumonia, graft rejection developed after transplantation, graft-versus-host diseases, autoiumune diseases, and so on. The hydroquinone derivative or pharmaceutically acceptable salt thereof is a non-steroidal material, and therefore advantageously exhibits no steroid-like side effect.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The present invention will be described in more detail with reference to the following examples.
EXAMPLE 1
6-Amino-5-(6-hydroxy-2,5,7,8-tetramethvlchroman-2-carboxamido)-3-methyl-1-phenyl-2,4 (1H. 3H)-pyrimidinedione
A mixture of 5,6-diamino-3-methyl-1-phenyl-2,4 (1H, 3H) -pyrimidinedione (3.02 g, 13 mmol), 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid (3.58 g, 14.3 mmol) and 4-(dimethylamino)pyridine (0.32 g, 2.6 mmol) was suspended in dichloromethane (60 mL). To the resultant suspension was added dropwise a solution of N, N'-dicyclohexylcarbodiimide (2.82 g, 13.7 mmol) indichloromethane (60 mL) at room temperature. The reaction mixture was stirred overnight and then filtered. The filtrate was concentrated and then subjected to silica-gel column chromatography, thereby giving the title compound (yield 57%). TOF-MS (Time-of-flight type mass spectrum): m/z 465 M+H!+ 1 H-NMR (CDC1 3 ):δ1.60(3H, s), 1.90-2.04(1H, m), 2.08(3H, s), 2.18(3H, s), 2.29(3H, s), 2.30-2.38(1H, m), 2.54-2.64(2H, m), 3.34(3H, s), 4.32(1H, s), 5.17(2H, bs), 7.27-7.36(2H, m), 7.53-7.60 (3H, m), 8.41 (1H, bs)
EXAMPLE 2
6-Amino-5-(6-hydroxy-2,5,7, 8-tetramethylchroman-2(R)-carboxamido)-3-methyl-1-phenyl-2,4(1pyrimidinedione
The title compound was prepared by repeating substantially the same procedure as Example 1, except using (R)-6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid as the intermediate having a chroman-type structure. The data of 1 H-NMR of the compound was compatible with those of the corresponding racemate obtained in Example 1.
α! d+ 59°(c=2,CHC1 3 )
EXAMPLE 3
6-Amino-5-(6-hydroxy-2,5,7,8-tetramethylchroman-2(S)-carboxamido)-3-methyl-1-phenyl-2,4 (1H, 3H) -pyrimidinedione
The title compound was prepared by repeating substantially the same procedure as Example 1, except using (S)-6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid as the intermediate having chroman-type structure. The data of 1 H-NMR of the compound was compatible with those of the corresponding racemate obtained in Example 1.
α! d- 59°(c=2, CHC1 3 )
EXAMPLE 4
6-Amino-1-(4-fluorophenyl)-5-(6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxamido)-3-methyl-2,4 (1H, 3H) -pyrimidinedione
The title compound was prepared by repeating substantially the same procedure as Example 1, except using 5,6-diamino-1-(4-fluorophenyl)-3-methyl-2,4 (1H, 3H)-pyrimidinedione.
TOF-MS: m/z 483 M+H!+ 1 H-NMR(CDC1 3 ):δ1.60(3H, s), 1.90-2.05(1H, m), 2.08(3H, s), 2.17(3H, s), 2.28(3H, s), 2.30-2.40(1H, m), 2.54-2.64(2H, m), 3.35(3H, s), 4.33(1H, s), 5.15(2H, bs), 7.30-7.43(4H, m), 8.43 (1H, bs)
EXAMPLE 5
6-Amino-1-(4-chlorophenyl)-5-(6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxamido)-3-methyl-2,4 (1H, 3H) -pyrimidinedione
The title compound was prepared by repeating substantially the same procedure as Example 1, except using 5,6-diamino-1-(4-chlorophenyl)-3-methyl-2,4 (1H, 3H)-pyrimidinedione.
TOF-MS: m/z 499 M+H! +
1 H-NMR(CDC1 3 ):δ1.60 (3H, s), 1.90-2.05 (1H, m), 2.07(3H, s), 2.18(3H, s), 2.29(3H, s), 2.30-2.40 (1H, m), 2.55-2.65(2H, m), 3.34(3H, s), 4.31(1H, s), 5.16(2H, bs), 7.31(2H, d, 8.4Hz), 7.53(2H, d, 8.4Hz), 8.40(1H, bs)
EXAMPLE 6
6-Amino-1-(2-chlorophenyl)-5-(6-hydroxy-2,5,7,8-tetramethvlchroman-2-carboxamido)-3-methyl-2,4 (1H, 3H) -pyrimidinedione
The title compound was prepared by repeating substantially the same procedure as Example 1, except using 5,6-diamino-1-(2-chlorophenyl)-3-methyl-2,4 (1H, 3H)-pyrimidinedione.
TOF-MS: m/z 499 M+H! +
1 H-NMR(CDC1 3 ):δ1.61(3H, s), 1.90-2.05(1H, m), 2.09(3H, s), 2.19(3H, s), 2.29(3H, s), 2.30-2.40(1H, m), 2.54-2.64(2H, m), 3.35(3H, s), 4.30(1H, s), 5.19(2H, bs), 7.40-7.55(3H, m), 7.55-7.65(1H, m), 8.40(1H, bs)
EXAMPLE 7
6-Amino-1-(3-chlorophenyl)-5-(6-hydroxy-2,5.7,8-tetramethylchroman-2-carboxamido)-3-methyl-2,4 (1H, 3H) -pyrimidinedione
The title compound was prepared by repeating substantially the same procedure as Example 1, except using 5,6-diamino-1-(3-chlorophenyl)-3-methyl-2,4 (1H, 3H)-pyrimidinedione.
TOF-MS: m/z 499 M+H! +
1 H-NMR (CDC1 3 ):δ1.60(3H, s), 1.90-2.04(1H, m), 2.08(3H, s), 2.18(3H, s), 2.29 (3H, s), 2.30-2.38(1H, m), 2.54-2.64(2H, m), 3.34(3H, s), 4.32(1H, s), 5.17(2H, bs), 7.38-7.65 (4H, m), 8.43 (1H, bs)
Example 8
6-Amino-5-(6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxamido)-3-methyl-l-(4-methylphenyl)-2,4 (1H, 3H) -pyrimidinedione
The title compound was prepared by repeating substantially the same procedure as Example 1, except using 5,6-diamino-3-methyl-1-(4-methylphenyl)-2,4 (1H, 3H)-pyrimidinedione.
TOF-MS: m/z 479 M+H! +
1 H-NMR(CDCl 3 ):δ1.60 (3H, s), 1.90-2.04(1H, m), 2.08(3H, s), 2.18(3H, s), 2.29(3H, s), 2.30-2.38(1H, m), 2.39(3H, s), 2.54-2.64 (2H, m), 3.34 (3H, s), 4.33 (1H, s), 5.18 (2H, bs), 7.20 (2H, d, 8.5 Hz), 7.34 (2H, d, 8.5 Hz), 8.40 (1H, bs)
EXAMPLE 9
6-Amino-5-(6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxamido)-1-(4-methoxyphenyl)-3-methyl-2,4 (1H, 3H)-pyrimidinedione
The title compound was prepared by repeating substantially the same procedure as Example 1, except using 5,6-diamino-1-(4-methoxyphenyl)-3-methyl-2,4 (lB, 3H)-pyrimidinedione.
TOF-MS: m/z 495 M+H! +
1 H-NMR(CDC1 3 ):δ1.60(3H, s), 1.90-2.05(1H, m), 2.10(3H, s), 2.19(3H, s), 2.29(3H, s), 2.30-2.40(1H, m), 2.55-2.65(2H, m), 3.35 (3H, s), 3.87 (3H, s), 4.34 (1H, s), 5.16 (2H, bs), 7.06 (2H, d, 9.0 Hz), 7.25 (2H, d, 9.0 Hz), 8.40 (1H, bs) cl EXAMPLE 10
6-Amino-5-(6-hydroxy-2,5,7, 8-tetramethylchroman-2-carboxamido)-1-phenyl-3-propyl-2,4 (1H, 3H)-pyrimidinedione
The title compound was prepared by repeating substantially the same procedure as Example 1, except using 5,6-diamino-1-phenyl-3-propyl-2,4 (1H, 3H)-pyrimidinedione.
TOF-MS: m/z 493 M+H! +
1 H-NMR(CDCl 3 ): δ0.85 (3H, t, 7.2 Hz), 1.48-1.58 (m, 2H), 1.60 (3H, s), 1.90-2.04 (1H, m), 2.08 (3H, s), 2.18 (3H, s), 2.29 (3H, s), 2.30-2.38 (1H, m), 2.54-2.64 (2H, m), 3.69-3.75 (2H, m), 4.32 (1H, s), 5.17 (2H, bs), 7.27-7.36 (2H, m), 7.53-7.60 (3H, m), 8.4 (1H, b)
EXAMPLE 11
5-(6-Hydroxy-2,5,7,8-tetramethvlchroman-2-carboxamido)-3-methyl-6-methylamino-1-phenyl-2,4 (1H, 3H) -pyrimidinedione
The title compound was prepared by repeating substantially the same procedure as Example 1, except using 5-amino-3-methyl-6-methylamino-1-phenyl-2,4 (1H, 3H)-pyrimidinedione.
TOF-MS: m/z 479 M+H! +
1 H-NMR(DMSO-d 6 ): δ1.46 (3H, s), 1.74--1.88 (1H, m), 2.00 (3H, s), 2.07 (3H, s), 2.12 (3H, s), 2.20-2.30 (1H, m), 2.55-2.65 (5H, m), 3.15 (3H, s), 7.25-7.35 (2H, m), 7.48-7.56 (3H, m), 8.5 (1H, b)
EXAMPLE 12
1-(4-Fluorophenyl)-6-dimethylamino-5-(6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxamido)-3-methyl-2,4 (1H, 3H)-pyrimidinedione
The title compound was prepared by repeating substantially the same procedure as Example 1, except using 5-amino-6-dimethylamino-1-(4-fluorophenyl)-3-methyl-2,4 (1H, 3H) -pyrimidinedione.
TOF-MS: m/z 511 M+H! +
1 H-NMR(DMSO-d 6 ): δ1.47 (3H, s), 1.75-1.90 (1H, m), 2.01 (3H, s), 2.08 (3H, s), 2.12 (3H, s), 2.20-2.30 (1H, m), 2.37 (6H, s), 2.54-2.64 (2H, m), 3.19 (3H, s), 7.30-7.43 (4H, m), 8.5 (1H, b)
EXAMPLE 13
6-Amino-5-(6-methoxy-2,5.7,8-tetramethylchroman-2-carboxamido)-3-methyl-1-phenyl-2,4 (1H, 3H)-pyrimidinedione
The title compound was prepared by repeating substantially the same procedure as Example 1, except using 6-methoxy-2,5,7,8-tetramethylchroman-2-carboxylic acid.
TOF-MS: m/z 479 M+H! +
1 H-NMR(CDCl 3 ): δ1.61 (3H, s), 1.90-2.04 (1H, m), 2.12 (3H, s), 2.21 (3H, s), 2.28 (3H, s), 2.30-2.38 (1H, m), 2.50-2.70 (2H, m), 3.35 (3H, s), 3.62 (3H, s), 5.18 (2H, bs), 7.27-7.36 (2H, m), 7.52-7.60 (3H, m), 8.42 (1H, bs)
EXAMPLE 14
5-(6-Acetoxy-2.5,7,8-tetramethvlchroman-2-carboxamido)-6-amino-3-methyl-1-phenyl-2,4 (1H, 3H)-pyrimidinedione
The compound of Example 1 (1.77 g, 3.80 mmol) and pyridine (0.154 mL, 1.90 mmol) were dissolved in dichloromethane (30 mL). To the resultant solution was added dropwise acetic anhydride (0.714 mL, 7.60 mmol) under ice cooling. The resultant reaction mixture was stirred overnight at room temperature, washed with 1N hydrochloric acid and 10% aqueous solution of sodium chloride successively, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was suspended in ethyl acetate and filtered to give the title compound (yield 87%).
TOF-MS: m/z 507 M+H! +
1 H-NMR(CDCl 3 ): δ1.65 (3H, s), 1.90-2.04 (1H, m), 1.93 (3H, s), 2.04 (3H, s), 2.28 (6H, s), 2.30-2.45 (1H, m), 2.50-2.70 (2H, m), 3.35 (3H, s), 4.69 (1H, b), 5.30 (1H, b), 7.26-7.35 (2H, m), 7.52-7.60 (3H, m), 7.89 (0.5H, b), 8.40 (0.5H, b)
EXAMPLE 15
6-Amino-3-methyl-1-phenyl-5- 4-(3,5,6-trimethyl -1,4-benzoquinon-2-yl )-2-hydroxy-2-methylbutyramido!-2,4 (1H, 3H)-pyrimidinedione
The title compound was obtained by repeating substantially the same procedure as Example 1, except using 4-(3,5,6-trimethyl-1,4-benzoquinon-2-yl)-2-hydroxy-2-methylbutyric acid which had been prepared by oxidation of 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid with ammonium cerium (IV) nitrate (yield 62%). The title compound was found in plasma a guinea pig as one of metabolites when the compound of Example 1 was orally administered to the guinea pig.
TOF-MS: m/z 481 M+H! +
1 H-NMR(CDCl 3 ): δ1.54 (3H, s), 1.63-1.75 (1H, m), 1.95-2.05 (1H, m), 1.97 (3H, s), 1.99 (3H, s), 2.01 (3H, s), 2.41-2.52 (1H, m), 2.63-2.73 (1H, m), 3.36 (3H, S), 4.11 (1H, s), 5.33 (2H, bs), 7.37-7.40 (2H, m), 7.52-7.63 (3H, m), 8.54 (1H, bs)
EXAMPLE 16
6-Amino-5- 4-(2,5-dihydroxy-3,4.6-trimethylphenyl)-2-hydroxy-2-methylbutyramido!-3-methyl-1-phenyl-2,4 (1H, 3H)-pyrimidinedione
The compound of Example 15 (0.48 g, 1.0 mmol) was dissolved in ethanol (3 mL). The resultant solution was stirred at room temperature overnight under hydrogen atmosphere in the presence of 10% Pd/C. The catalyst in the solution was filtered off, and the filtrate was concentrated under reduced pressure to give the title compound.
ESI-MS (Electro-spray-ionization mass stectrum):
m/z 483.21 M+H! +
EXAMPLE 17
6-Amino-5- (6-hydroxy-2,5,7,8-tetramethyl-2-chromanylmethyl)amino!-3-methyl-1-phenyl-2,4 (1H, 3H) -pyrimidinedione
The compound of Example 14 (64 mg, 1.0 mmol) was dissolved in THF (10 mL). To the resultant solution was added borane-methyl sulfide complex (10 M, 0.24 mL, 2.4 mmol). The resultant reaction mixture was refluxed for 5 h. To the resultant was added 1N hydrochloric acid (2.4 mL) under ice-cooling. The resultant mixture was refluxed for 2 h, followed by concentration under reduced pressure. The residue was extracted with dichloromethane after addition of 1N aqueous solution of sodium hydroxide. The organic layer was washed with 10% aqueous solution of sodium chloride, dried over anhydrous sodium sulfate, and concentrated under reduced pressure. The residue was crystallized by addition of ethyl acetate and ether to give the title compound (yield 35%).
TOF-MS: m/z 451 M+H! +
1 H-NMR(CDCl 3 ): δ1.24 (3H, s), 1.65-1.80 (1H, m), 2.05 (3H, s), 2.10 (3H, s), 2.12 (3H, s), 1.95-2.20 (1H, m), 2.60-2.70 (2H, m), 3.02 (2H, bs), 3.36 (3H, s), 4.24 (1H, s), 4.78 (2H, bs), 7.25-7.35 (2H, m), 7.50-7.60 (3H, m)
EXAMPLE 18
6-Amino-5- N-(6-hydroxy-2,5,7,8-tetramethyl-2-chromanylmethyl)aminomethyl!-3-methyl-1-phenyl-2,4 (1H, 3H) -pyrimidinedione
6-Amino-3-methyl-1-phenyl-2,4 (1H, 3H)-pyrimidinedione (5.00 g, 23 mmol) was suspended in dimethylformamide (77 ml). To the resultant suspension was added phosphorus oxychloride (2.57mL,27.6 mmol), and the resultant mixture was reacted at 60° C. for 3 h. The reaction mixture was diluted with water, and adjusted to ca. pH 12 with sodium hydroxide. The precipitates formed in the reaction mixture was filtered to give a crude product. The crude product was recrystallized from a mixture of ethanol, ethyl acetate and water to give an aldehyde, 6-amino-5-formyl-3-methyl-1-phenyl-2,4 (1H, 3H)-pyrimidinedione (yield 75%).
To a solution of 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxamide (1.0 g, 4.0 mmol) in THF (30 mL) was added boranemethyl sulfide complex (10 M, 1.9 mL, 19 mmol). The resultant mixture was refluxed for 7 h. To the resultant reaction mixture was added IN hydrochloric acid (9.6 mL) under ice-cooling, and the resultant mixture was further refluxed for 2 h followed by concentration under reduced pressure. The residue was extracted with ethyl acetate after addition of 1N aqueous solution of sodium hydroxide. The organic layer was washed with 10% aqueous solution of sodium chloride, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and purified by silica-gel column chromatography to give an amine, 2-aminomethyl-6-hydroxy-2,5,7,8-tetramethylchroman (yield 55%).
The aldehyde (204 mg, 0.83 mol) and the amine (353 mg, 1.25 mol) thus prepared were dissolved in dichloroethane (4 mL), and the solution was heated at 70° C. for 7 h to react with one another. The resultant reaction mixture was cooled to room temperature and then sodium triacetoxyborohydride (352 mg, 1.66 mmol) was added thereto. The mixture was allowed to react at room temperature overnight. The reaction mixture was acidified with diluted hydrochloric acid, adjusted to pH 8-9 with sodium hydroxide, and then extracted with dichloromethane. The organic layer was washed with 10% aqueous solution of sodium chloride, dried over anhydrous sodium sulfate, concentrated under reduced pressure, and then crystallized from ethyl acetate/ethanol to give the title compound (yield 26%).
TOF-MS: m/z 466 M+H! +
1 H-NMR (DMSO-d 6 ): δ1.09 (3H, s), 1.40-1.60 (1H, m), 1.99 (3H, s), 2.03 (3H, s), 2.07 (3H, s), 1.85-2.15 (1H, m), 2.50-2.80 (4H, m), 3.12 (3H, s), 3.56 (1H, d, 12 Hz), 3.75 (1H, d, 12Hz), 5.40 (2H, bs), 7.10-7.26 (2H, m), 7.40-7.55 (3H, m)
EXAMPLE 19
6-Amino-5-(N-butyl-6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxamidomethyl)-3-methyl-1-phenyl-2,4 (1H, 3H)-pyrimidinedione
Reductive amination of 6-amino-5-formyl-3-methyl-1-phenyl-2,4 (1H, 3H)-pyrimidinedione with N-butylamine was performed in substantially the same manner as Example 18 to thereby give an intermediate, 6-amino-5-(N-butylaminomethyl)-3-methyl-1-phenyl-2,4 (1H, 3H)-pyrimidinedione. The intermediate was reacted with 6-hydroxy-2,5,7,8-tetramethylchroman-2-carboxylic acid by a conventional condensation method to give the title compound (yield 36%).
1 H-NMR (CDCl 3 ): 67 0.95 (3H, t, 7.2 Hz), 1.33 (2H, t of q, 7.2 Hz, 7.2 Hz), 1.57 (3H, s), 1.60-1.75 (3H, m), 2.03 (3H, s), 2.15 (3H, s), 2.17 (3H, s), 2.45-2.68 (3H, m), 2.45-2.65 (2H, m), 3.32 (3H, s), 3.52-3.67 (1H, m), 3.80-3.95 (1H, m), 4.28 (1H, bs), 4.41 (1H, d, 16 Hz), 4.52 (1H, d, 16 Hz), 5.85 (b), 7.13-7.32 (2H, m), 7.48-7.60 (3H, m)
Evaluation 1: Inhibition of picryl chloride-induced dermatitis
Effect of the compounds of the present invention on picryl chloride-induced dermatitis, which is a typical model of type IV allergic inflammation, was estimated by the Asherson's method Immunology, 15, 405 (1968)! in the following manner.
A 7% (w/v) solution of picryl chloride in acetone (0.1 mL) was applied on a portion of the abdominal skin of each of ICR male mice to sensitize the mice. After 7 days, a 1% (w/v) solution of picryl chloride in acetone (0.02 mL) was applied on the ears of the individual mice to induce allergic reaction. Just after the challenge, 0.04 mL of acetone (control) or a 0.25-2.5% (w/v) solution of the test compound in acetone was applied on the ear. Increase of the ear thickness of the individual mice was measured at 24 h after the challenge, and inhibitory effect of the test compound on the dermatitis was estimated based on the difference in ear thickness between before and after the induction of the allergic reaction.
The hydroquinone derivative of the present invention had inhibitory effect on swelling as exemplified below. The results show that the hydroquinone derivative of the present invention is effectively absorbed through skin and inhibits dermatitis at the diseased portion by percutaneous administration.
______________________________________Compound Concentration (%) Inhibition (%)______________________________________Example 1 0.25 69Example 2 0.75 65Example 3 0.75 69Example 11 0.75 44Example 13 2.50 33Example 14 0.75 53Example 15 0.75 70Example 17 0.75 80Example 19 0.25 49______________________________________
Evaluation 2: Inhibition of albumin-induced asthma
Effect of the compounds of the present invention on albumin-induced asthma was estimated in the following manner.
Inhalation of 1% ovalbumin using ultrasonic nebulizer into Hartley male guinea pigs was performed 10 min/day over 8 days to sensitize the guinea pigs. One week after the last sensitization, inhalation of 2% ovalbumin was performed for 5 min. to induce allergic reaction. Metyrapone (10 mg/kg, i.v.) was administered at 24 h and 1 h before the challenge, propylene glycol (control) or a solution of the test compound in propylene glycol was orally administered at 1 h before and 3 h after the challenge, and pyrilamine (10 mg/kg, i.p.) was intraperitoneally administered at 30 min before the challenge. Air way resistance was measured by double flow plethysmography at 1 min, 4 h, 5 h, 6 h, 7 h, and 8 h after the challenge, and inhibitory effect of the test compound on the asthma was estimated based on the measurements obtained.
As a result, the compound of Example 1 (100 mg/kg) showed 62% inhibition on the air way reaction at 1 min after the challenge, and 50% inhibition on the air way reaction (AUC) during 4-8 h after the challenge. The results show that the hydroquinone derivative of the present invention is effectively absorbed through the digestive tract and inhibits asthma by oral administration.
Formulation 1: Water soluble ointment
Water soluble ointment of the following formulation was prepared by a conventional manner.
______________________________________Contents in 2 g of the ointment______________________________________The compound of Example 1 40 mgPoly(ethylene glycol) 400 1372 mgPoly(ethylene glycol) 4000 588 mg______________________________________
Formulation 2: Tablets for oral administration
Tablets of the following formulation were prepared by a conventional manner.
______________________________________Contents in a tablet______________________________________The compound of Example 1 100 mgLactose 353 mgCalboxymethylcellulose calcium 30 mgHydroxymethylcellulose 7 mgMagnesium stearate 5 mgCrystalline cellulose 5 mg______________________________________ | Disclosed is a hydroquinone derivative or a pharmaceutically acceptable salt thereof, the hydroquinone derivative being represented by formula (I): ##STR1## wherein R 1 is a phenyl group which is unsubstituted or substituted with a substituent or substituents each independently selected from the group consisting of a halogen atom, a C1-4 alkyl group and a C1-4 alkoxy group;
R 2 is a hydrogen atom or a C1-4 alkyl group;
each of R 3 and R 4 is independently a hydrogen atom or a C1-4 alkyl group;
R 5 is a hydrogen atom or a C1-4 alkyl group;
each of R 6 , R 7 and R 8 is independently a hydrogen atom or a C1-4 alkyl group;
P is a hydroxyl group;
Q is a hydroxyl group, a C1-4 alkoxy group, a C1-18 acyloxy group or an oxo group;
P may form together with Q an ether bond;
R is a hydroxyl group, a C1-4 alkoxy group, a C1-18 acyloxy group or an oxo group, provided that when one of said Q and said R is an oxo group, the other is also an oxo group;
X is a single bond, an --NR 10 --group or a --CH 2 --NR 10 --group in which R 10 is a hydrogen atom or a C1-4 alkyl group;
Y is a methylene group or a carbonyl group; and
dotted bonds in a six membered ring represent that said six membered ring has the maximum number of double bonds. | 2 |
FIELD OF THE INVENTION
[0001] The present invention is related to a method of continuous cooking and washing of cellulose-bearing raw material, especially wood chips, by using an improved liquor circulation pattern. More particularly, the present invention relates to a digester provided with the screens and piping necessary for carrying out this method.
BACKGROUND OF THE INVENTION
[0002] A continuous digester for pulp manufacture is generally a vertical, essentially cylindrical vessel, receiving a feed of cellulose-bearing raw material (for example, wood chips) in the top of the digester and discharging cooked chips, i.e. pulp, from the bottom of the digester. The vessel is usually a pressure vessel, although this disclosure is not limited to such vessels. At one or several points along the digester, going downwards from the top, there may be an increase in digester diameter. Adjacent such a diameter increase, and generally below it, there is typically an annular screen structure in the vessel inner wall. Through this screen structure, liquor is removed from the downward moving chip column by means of a pressure difference. This liquor can be returned into the process by pumping it back into the digester in the middle of the descending chip column through a central pipe, either above the screen (whereby co-current circulation is generated) or below the screen (providing counter-current circulation). The circulating liquor is heated, and appropriate chemicals and liquids may be added to it to achieve the desired chemical and thermal conditions for the chip column moving downwards past the screen structure. The liquor flowing out through the screen structure can also be finally withdrawn from the digester to be reprocessed at another location. As such extracted liquor is no longer returned to the digester, it is replaced with e.g. washing filtrate from a downstream washing plant. The filtrate is generally pumped into the bottom of the pressurized digester. This washing liquor is forced to flow counter-currently upwards through the packed column to exit through the above-mentioned extraction screens, and is further conducted to reprocessing.
[0003] In a prior art cooking method, part of this washing liquor is added to the circulation flows together with cooking chemicals, and a corresponding amount of liquor is extracted from the circulation screens for reprocessing. The general aim is to replace the liquor affecting the chips passing the circulation screens. In this method, the amount of washing liquor to be added to the digester bottom is correspondingly reduced. This assists the downward movement of the chip column, because the counterforce created by the washing filtrate flowing upward through the chip bed is reduced.
[0004] A problem associated with the above-mentioned designs is the radial flow of liquor through the chip bed from the central pipe towards the screen structure at the digester wall. The chip column causes a dynamic pressure loss for radial flow, this loss being dependant on the flow rate. This results in a force vector in the radial direction, which force pushes the chip bed against the screen structure. Because the chip bed is flexibly subject to any force, this dynamic radial force causes thickening, i.e. packing of the chip column against the screen structure at the vessel inner wall, which in turn results in an increased dynamic pressure loss, etc. If the screen structure at the digester wall is overloaded by the liquid flow through the chip column, the screen structure is blocked very quickly, and there will be disturbances in the process; the movement of the chip column may even stop, resulting in production losses.
[0005] When a screen as described above is used for extraction only, without a circulation flow to displace the extraction liquor, a zone of zero liquid velocity appears in the middle of the digester. Therefore, in the counter-current washing zone of the digester, the washing efficiency remains lower in the middle of the digester than close to the digester wall.
[0006] There have been attempts to solve this problem using a so-called quench circulation. The washing liquor, flowing from the digester bottom upwards to the extraction screens, was removed through dedicated quench circulation screens, situated below the extraction screens. This removed liquid was pumped through the central pipe into the middle of the digester above the extraction screens. From there, the liquor was supposed to flow towards the extraction screens to displace the more concentrated cooking liquor to reprocessing. This quench circulation flow, however, increased the amount of liquor flowing from the center of the digester towards the extraction screens, as well as its radial flow velocity, which increased the non-desired chip column packing against the extraction screens. The additional load due to the quench circulation worsened the operation of the screens in the loaded digesters and the movement of the chip column. Therefore, this design has been abandoned and the vacant quench circulation screens have in general been connected in parallel to the extraction screens to reduce the load of the latter.
[0007] Due to the problems described above, circulations or extraction flows in the digester cannot be maintained at sufficiently high rates, which results in non-desired chemical and temperature gradients. This has a negative impact on the quality of the product and the production economy. In the worst case, the operation of the whole digester may stall due to screen blockages.
[0008] Solutions for the problem have been presented for example in U.S. Pat. Nos. 2,998,064; 3,385,753; and 6,129,816. The aim of these patents is to reduce the chip column compaction at the screen area by means of the screen construction itself, and simultaneously to prevent the screen from blocking and to thus improve the digester operation. Because the above-mentioned patents cannot repeal the laws of physics, i.e. the increase of chip column compaction against the screen caused by radial flow, the advantage of the methods disclosed in these patents is small and possibly non-existent.
[0009] In U.S. Pat. No. 3,475,271, a digester essentially for sawdust pulping is disclosed. In the immediate proximity of its bottom, in the middle of the digester, there is a rotating central screen, which is either cylindrical, or a cone the diameter of which increases in the plug flow direction of the chip column. Washing liquor to be added into the digester is pumped through a screen at the pressure vessel wall and flows horizontally towards the mentioned central screen, through which it is extracted to reprocessing. The aim of this arrangement is to carry out horizontal-displacement washing at the digester bottom. Physics causes problems in this design as well, as does the location of the screen in relation to the supply of wash liquid. The flow from the wall of the vessel towards its center encounters a decreasing flow area, which means increasing flow velocity. Consequently, the radial force vector towards the screen in the middle of the digester increases very quickly, even with small liquor flow rates (compared with flow in the opposite direction, from the middle towards the wall). Because of this, a central screen according to U.S. Pat. No. 3,475,271 blocks very easily. To be able to force the required amount of liquid from the distribution screen at the wall of the digester to the screen in the middle of the digester, both screens have to be very high in proportion to the digester volume, which makes this construction expensive. That is why this design has not been supplied commercially for decades.
SUMMARY OF THE INVENTION
[0010] In accordance with the present invention, these and other objects have now been accomplished by the development of a method for continuously producing pulp from lignocellulose-containing material in a digester including a top, a bottom, and a central pipe extending from the top to the bottom within the digester, at least one central screen assembly disposed on the central pipe, and a wall screen assembly disposed along the inner wall of the digester, the method comprising feeding a porous column of the lignocellulose-containing material from the top of the digester to the bottom of the digester, pumping liquor through the porous column of the lignocellulose-containing material in a predetermined direction, and simultaneously withdrawing the liquor through the at least one central screen assembly and the wall screen assembly. Preferably, the predetermined direction is concurrent, countercurrent, or a radial direction.
[0011] In accordance with one embodiment of the method of the present invention, the wall screen assembly and the central screen assembly are disposed at substantially the same level within the digester.
[0012] In accordance with another embodiment of the method of the present invention, the method includes withdrawing a plurality of separate streams of the liquor through the central screen assembly. Preferably, the central screen assembly comprises a plurality of distinct central screens.
[0013] In accordance with another embodiment of the method of the present invention, the method includes recirculating at least a portion of the withdrawn liquor to the digester through a circulation loop. Preferably, the method includes heating or supplying chemicals to the recirculating portion of the withdrawn liquor in the circulation loop.
[0014] In accordance with another embodiment of the method of the present invention, the digester includes a withdrawal screen disposed along the inner wall of the digester, and the method includes adding washing liquor to the digester adjacent to the withdrawal screen through the central pipe, whereby the washing liquor displaces the liquor through the withdrawal screen, and displacing at least a portion of the washing liquor through the central screen assembly by the washing liquor flowing countercurrent through the lignocellulose-containing material.
[0015] In accordance with the present invention, these and other objects have also been accomplished by the development of a digester for continuously producing pulp from lignocellulose-containing material, the digester having a top and a bottom and comprising a top inlet for feeding the lignocellulose-containing material into the top of the digester, a bottom outlet for removing the cooked lignocellulose-containing material from the bottom of the digester, at least one wall screen assembly disposed along the inner wall of the digester for withdrawing liquor from the lignocellulose-containing material, a central pipe extending from the top to the bottom of the digester, and at least one annular central screen disposed on the central pipe for withdrawing liquor therethrough complementary with that of the at least one wall screen assembly. Preferably, the at least one annular central screen comprises a cylindrical central screen.
[0016] In another embodiment, the at least one annular central screen comprises a conical central screen.
[0017] In accordance with one embodiment of the digester of the present invention, the digester includes back-flushing means associated with the at least one annular central screen.
[0018] In accordance with another embodiment of the digester of the present invention, the central pipe includes an inlet for introducing washing liquor into the digester, the inlet being disposed adjacent to the at least one wall screen assembly.
[0019] According to the present invention, the excessive packing of chips in a moving column against an individual screen, and the zone of zero velocity in the middle of the digester, are avoided by using a screen assembly located on the central tube or pipe for liquor withdrawal together with a wall screen. The required outflow is thus divided between the wall screen and the central screen. In a preferred embodiment, the central screen is essentially at the same level as the wall screen.
[0020] The central withdrawal screen structure in the middle of the pressure vessel may be located at a level different from that of the complementary wall screen assembly. In this case, it is so located that liquid flowing towards this central screen has to travel upwards through the chip column, and against the direction of the plug flow. This counter-flow reduces the chip column compaction against the central screen, especially at the bottom part of the screen, and the screen remains open and operational.
[0021] With the screen solutions according to the present invention, the amount of circulation or extraction flows can be increased in proportion to the pulp production rate without increasing the load of an individual screen so much that it would disturb the movement of the chip column and have a negative influence on the quality and quantity of product.
[0022] The present invention is applicable for all types of continuous digesters having various different circulation and extraction flow patterns, found on the market under a variety of commercial names.
[0023] The present invention can be applied in continuous cooking both for the cooking vessel and the impregnation vessel. These vessels can be pressurized or un-pressurized.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] The present invention is described in more detail with reference to the following detailed description, which, in turn, refers to the appended drawings, in which:
[0025] FIG. 1 is a side, elevational, partially schematic view showing the general operational principles of a typical single-vessel, hydraulic, continuous digester of the prior art;
[0026] FIG. 2 is a side, elevational, partially schematic view of one embodiment of the present invention, in which the extraction flow is divided into two parts, i.e. between the central screen in the middle of the pressure vessel and the screen structure at the wall of the pressure vessel; and
[0027] FIG. 3 is a side, elevational, partial, enlarged schematic view of a digester profile of the extraction screen region, and how the present invention is applied to improve the washing in the digester.
DETAILED DESCRIPTION
[0028] FIG. 1 shows the general outline of a prior art continuous hydraulic digester. It consists of a pressure vessel ( 11 ), upper and lower cooking circulation screens ( 12 ), mounted to the upper part of the pressure vessel ( 11 ), extraction screens ( 13 ) mounted close to the middle part of the vessel, and optional washing circulation screens ( 14 ) mounted close to the bottom of the pressure vessel. Along the vertical center line of the vessel ( 11 ) there is typically a central pipe ( 15 ), which comprises a single pipe or several nested pipes. Through this central pipe, separate circulation entry flows are conveyed to different levels of the vessel ( 11 ). General liquid flow directions inside the pressure vessel ( 11 ) toward the extraction screens ( 13 ) are shown by arrows ( 21 ). The chips to be cooked and the liquid cooking chemical are introduced into the upper part of the pressure vessel ( 11 ) through a feed line ( 1 ). In the pressure vessel ( 11 ), the chips form a porous chip column, the porosity of which changes from the top down. The void space between the chips enables the flow of cooking liquor in desired directions inside the chip column as pressure differences are generated. The upper part of the pressure vessel ( 11 ) is typically an impregnation zone with a relatively low temperature. In this zone, the required cooking chemicals are impregnated into the chips. The chip column moving downwards and the cooking liquor flowing in its voids are heated by circulating this cooking liquor through the cooking circulation screens ( 12 ) using upper cooking circulation ( 2 ) and lower cooking circulation ( 3 ). The upper cooking circulation ( 2 ) liquor is typically withdrawn from the upper screen ( 12 A) and returned through the central piping at a position above that screen.
[0029] Correspondingly, the lower circulation ( 3 ) liquor withdrawn from the lower screen ( 12 B) is returned at a position in the screen zone as shown. The circulating liquors in the cooking circulation ( 2 ) and ( 3 ) are heated to the desired cooking temperature. Equipment required for pumping and heating the circulating liquor and/or addition of different chemicals and/or washing filtrate is not shown in FIG. 1 .
[0030] In the zone between the cooking circulation screens ( 12 ) and extraction screens ( 13 ) cooking reactions occur, resulting in softening of the chips. The gravitational force caused by the chip column height and the dynamic forces created by liquor flows, together with weakening of the mechanical strength of chips, result in increased compaction of the chip column, i.e. decrease of void space between the chips and of the relative proportion of voids in the digester volume. The maximum compaction of the chip column is typically at the extraction screen ( 13 ), where the vertical velocity vectors of the cooking liquor ( 21 ) flowing downwards and the washing liquid ( 22 ) flowing upwards amount to zero. The maximum region of zero velocity ( 0 ) in the middle of the digester is also created at the same level. This region of zero velocity ( 0 ) weakens the efficiency of liquor displacements in the digester. Liquid consisting of cooking liquor ( 21 ) and displacing washing liquid ( 22 ), exits through the extraction screens ( 13 ) and is conveyed to reprocessing along line ( 4 ).
[0031] Counter-current washing of the cooked chips is carried out in the zone between the extraction screens ( 13 ) and the washing circulation screens ( 14 ). Washing liquid, which has been pumped to the bottom part of the pressure vessel ( 11 ) through line ( 7 ), is first heated by means of washing circulation ( 5 ) to a desired value and re-enters the digester through the lower end of the central pipe. Subsequently, the upwards-flowing washing liquid displaces less pure cooking liquor towards the extraction screens ( 13 ). Because the flow occurs by the action of pressure difference, the developing flow direction in the case shown in FIG. 1 is parallel to the straight line between the lower end of the central pipe and the extraction screens ( 13 ). In the shaded region of zero velocity ( 0 ) in the middle of the digester, no direct displacement of liquors occurs. If the digester is not equipped with washing circulation ( 5 ), this region of zero velocity is even larger than in the case shown.
[0032] FIG. 2 shows an embodiment in accordance with the present invention, in which a central screen ( 16 ) has been added to the central pipe ( 15 ) of the digester design according to FIG. 1 . This screen is located essentially in the middle of the vessel ( 11 ) at the approximate level of the extraction screens ( 13 ). The liquor extracted through the central screen ( 16 ) is conveyed through line ( 9 ) to reprocessing. A new flow channel can be installed for line ( 9 ) in the central pipe ( 15 ), or existing flow channels can be used if such channels have possibly been left free following with some change, such as the removal of the above described quench circulation. The area of the central screen ( 16 ), mainly its height, is defined on the basis of the amount of liquor to be extracted through the central screen ( 16 ). This extracted liquor amount is preferably nearly as large, and more preferably essentially equal to the liquor amount extracted through the extraction screens ( 13 ). The position of the upper part of the central screen ( 16 ) in relation to the upper part of the extraction screens ( 13 ) affects the uniformity of the cooking result. In the case shown in FIG. 2 , it is preferable that the upper part of the central screen ( 16 ) is above the upper edge of the extraction screen ( 13 ), because there is always a higher temperature in the middle of the pressure vessel ( 11 ) than next to its wall. This temperature difference is due to heating circulations (e.g. circulation ( 2 ) and ( 3 )) and heat losses through the pressure vessel wall ( 11 ).
[0033] The cooking reactions are terminated earlier in the central part of the pressure vessel ( 11 ) than at the periphery, as hot cooking liquor ( 21 ) is removed from the central part of the digester through the central screen ( 16 ), and somewhat cooler cooking liquor ( 21 ) closer to the wall zone is withdrawn later through the extraction screen ( 13 ). Cooking has then taken place at a slightly higher temperature in the middle of the pressure vessel ( 11 ) than at the wall, but during a correspondingly shorter period. This results in a uniform cooking result across the whole cross-section of the vessel ( 11 ).
[0034] The length of the central screen ( 16 ) is determined according to the capacity required. If a washing circulation ( 5 ) is used as shown in FIG. 2 , the central screen ( 16 ) should not extend too near the inlet of the washing circulation in the middle of the digester, because there is a risk of short-cut flow from the washing circulation inlet directly to the central screen ( 16 ). If a plurality of liquor fractions are to be extracted through the central screen ( 16 ), it is divided into distinct sections with individual outlet channels, or a corresponding number of distinct screens is used. For example, cooking liquor ( 21 ) can be withdrawn through the upper part of the central screen ( 16 ) and washing liquor ( 22 ) through its lower part in desired proportions. Cooking and washing processes can thus be adjusted independently. If necessary, a blocked central screen ( 16 ) can be cleared by backflushing, in which liquor is momentarily pumped backwards at a high velocity. This backflushing liquor can be brought backwards along line ( 9 ), or a separate flow channel (not shown in the figure) with appropriate control equipment can be provided for it in association with the central pipe structure ( 15 ).
[0035] It is particularly advantageous to apply the present invention to a digester design having no washing circulation ( 14 ) in the bottom part of the pressure vessel ( 11 ), because washing liquid ( 22 ) in such digester designs has a particular tendency to channel, that is to flow directly from the entry point of the washing liquid ( 22 ) towards the extraction screens ( 13 ).
[0036] FIG. 3 shows an embodiment of the present invention, in which improved washing is achieved in the extraction screens. In this embodiment, washing liquid ( 23 ), which is either washing circulation ( 14 ) liquid or fresh washing liquid from line ( 7 ), see FIG. 2 , is supplied through a flow channel of the central pipe ( 15 ), and enters the digester through a distributing section of the central pipe ( 15 A) above the extraction screens ( 13 ). This washing liquid ( 23 ) displaces the cooking liquor ( 21 ) from the chip column through the extraction screen ( 13 ). This relatively cool washing liquid ( 23 ) terminates the cook effectively and evenly at the extraction screen ( 13 ). Because washing liquor ( 23 ) is also cleaner than the bound cooking liquor inside the chips, diffusion starts immediately due to the concentration difference. The liquor and fibers inside the chips become cleaner, and the washing liquor ( 23 ) in the chip column voids carries the impurities. Diffusion time for the descending chip column is created by means of a non-screen part ( 15 B) in the central pipe, located between the section for addition of washing liquor ( 23 ) in the central pipe ( 15 A) and a central screen ( 15 C) in accordance with the above disclosure. When the chip column descends towards the bottom part of the pressure vessel, impure washing liquor is displaced from the voids of the chip column by counter-currently rising washing liquor ( 22 ). The displaced washing liquor ( 23 ) and part of the displacing washing liquor ( 22 ) are conveyed out of the vessel along a flow channel in the central pipe ( 15 ).
[0037] Using the disclosed method, pulp can be cooked and washed evenly.
[0038] Although the invention herein has been described with reference to particular embodiments, it is to be understood that these embodiments are merely illustrative of the principles and applications of the present invention. It is therefore to be understood that numerous modifications may be made to the illustrative embodiments and that other arrangements may be devised without departing from the spirit and scope of the present invention as defined by the appended claims. | Methods for continuously producing pulp from lignocellulose-containing material in a digester are disclosed in which the porous lignocellulose-containing material is fed from the top to the bottom of the digester, liquor is pumped through the porous column of lignocellulose-containing material in a predetermined direction, and liquor is simultaneously withdrawn through at least one central screen assembly and through a wall screen assembly. A digester for continuously producing pulp from lignocellulose-containing material is also disclosed. | 3 |
BACKGROUND OF THE INVENTION
FIELD OF THE INVENTION
[0001] The present invention relates to controlled-environment cargo containers, and more particularly to a method and apparatus for controlling components of a cargo container's environment, for example temperature and humidity.
SUMMARY OF THE INVENTION
[0002] The present invention is directed to configuring cargo containers to promote a horizontal flow in the container environment. As an additional benefit, when containers are so configured, certain expensive and ineffective components typically required in conventional containers may be omitted.
BRIEF DESCRIPTION OF THE DRAWINGS
[0003] These and other objects, features and advantages of the present invention will become more readily apparent upon considering the following detailed description of specific embodiments, with reference to the accompanying drawings where like numbers reference like elements, in which:
[0004] FIG. 1 is a perspective side view of a cargo container according to one embodiment of the present invention;
[0005] FIG. 2 is a transverse sectional view of the cargo container of FIG. 1 , looking from a second end toward a first end;
[0006] FIG. 3 is a plan sectional view of the cargo container of FIG. 1 , a horizontal cutting plane passing through a roof assembly;
[0007] FIG. 4 is a longitudinal sectional view of the cargo container of FIG. 1 , looking from a second side toward a first side, a vertical cutting plane having removed the first side from this view;
[0008] FIG. 5 is a longitudinal sectional view of a cargo container according to a second embodiment of the invention, looking from a second side toward a first side, a vertical cutting plane having removed the first side from this view;
[0009] FIG. 6 is a longitudinal sectional view of a cargo container according to a third embodiment of the invention, looking from a second side toward a first side, a vertical cutting plane having removed the first side from this view;
[0010] FIG. 7 is a plan sectional view of a cargo container according to a fourth embodiment of the invention, a horizontal cutting plane passing through a roof assembly;
[0011] FIG. 8 is a plan sectional view of a cargo container according to a fifth embodiment of the invention, a horizontal cutting plane passing through a roof assembly; and
[0012] FIG. 9 is a plan sectional view of a cargo container according to a sixth embodiment of the invention, a horizontal cutting plane passing through a roof assembly.
DETAILED DESCRIPTION
[0013] 1. Structure
[0014] Referring first to FIGS. 1 through 4 , a cargo container according to one embodiment of the present invention is generally illustrated at 10 . The cargo container includes a roof assembly 12 , a floor assembly 14 , first and second opposing side assemblies 16 , 18 , and first and second opposing end assemblies 20 , 22 that cooperate to form an enclosed cargo compartment 24 . It will be appreciated that the cargo compartment 24 could be enclosed by a different arrangement of assemblies without departing from the spirit of the invention. In this embodiment, the second end assembly includes a door sub-assembly 26 which has an open position to provide access to the cargo compartment 24 and an alternative closed position to seal the cargo compartment 24 .
[0015] At least one of the first and second side assemblies 16 , 18 includes a lateral portion 28 within the cargo compartment 24 .
[0016] The cargo container 10 further includes a supply-conduit 30 adjacent the lateral portion 28 of the cargo compartment 24 . The supply-conduit 30 is placed, arranged, fitted and otherwise adapted to receive therewithin a fluid from outside the cargo compartment 24 . In this embodiment, the supply-conduit 30 is formed integrally from the structure of the cargo container 10 , and more particularly is illustrated as an integral portion of the first side assembly 16 .
[0017] The supply-conduit 30 includes a vent 32 passing radially therethrough and adapted to conduct the fluid within the supply-conduit 30 into the cargo compartment 24 . In this embodiment, the fluid conducted by the supply-conduit is substantially air.
[0018] Although the supply-conduit 30 is operable so as to ventilate the cargo compartment 24 with fluid received from outside the cargo compartment 24 , the cargo container 10 may also include a controller 34 having an input port 36 adapted to receive a fluid and an output port 38 adapted to supply the fluid received at the input port 36 . The controller 34 is operable to urge an environmental component of the fluid supplied at the output port 38 toward a desired value. For example, the controller 34 might include a heater 40 for increasing the temperature of the fluid, a cooler 42 for decreasing the temperature of the fluid, a humidifier 44 for increasing the humidity of the fluid, or a dehumidifier 46 for decreasing the humidity of the fluid. These aspects are shown diagrammatically in FIG. 2 , for example. In this embodiment, the output port 38 of the controller 34 is connected to supply fluid to the supply-conduit 30 so as to provide more control over the environment within the cargo compartment 24 .
[0019] The cargo container 10 may additionally include a return-conduit 50 having a first end 52 connected to the cargo compartment 24 and a second end 54 connected to the input port 36 of the controller 34 . So arranged, the return-conduit 50 is operable to conduct fluid from the cargo container 24 to the controller 34 , so as to form a closed system with the supply-conduit 30 and the controller 34 for controlling and recirculating fluid. In this embodiment, the return-conduit 50 follows along the roof assembly 12 ; however, other placements would be possible without departing from the spirit of the invention.
[0020] The cargo container 10 may further include a pump or fan 56 connected in series with the supply-conduit 30 , the controller 34 and the return-conduit 50 . The pump or fan 56 is operable to provide additional motive force for circulating the fluid, beyond any thermodynamic forces otherwise present in the passive system formed by the supply-conduit 30 , the controller 34 and the return-conduit 50 .
[0021] Finally, because no ducting need follow along the floor assembly 14 , there is no need to include T-rail floor panels. Thus in this embodiment, the floor assembly 14 includes a simple and robust corrugated floor 58 .
[0022] Referring now to FIG. 5 , a cargo container according to a second embodiment of the invention is generally illustrated at 10 a . In this embodiment, the vent 32 a is elongated and oriented substantially vertically within the cargo compartment 24 a . The vent 32 a may extend substantially from the top of the cargo compartment 24 a proximate the roof assembly 12 a to the bottom of the cargo compartment 24 a proximate the floor assembly 14 a . The vent 32 a defines a plurality of holes 60 a through the supply-conduit 30 a that are each adapted to conduct fluid within the supply-conduit 30 a into the cargo compartment 24 a.
[0023] Referring now to FIG. 6 , a cargo container according to a third embodiment of the invention is generally illustrated at 10 b . In this embodiment, the vent 32 b is also elongated and oriented substantially vertically within the cargo compartment 24 b and may extend substantially from the top of the cargo compartment 24 b proximate the roof assembly 12 b to the bottom of the cargo compartment 24 b proximate the floor assembly 14 b . However, in this third embodiment, the vent 32 b defines an elongated slot 60 b through the supply-conduit 30 b that is adapted to conduct fluid within the supply-conduit 30 a into the cargo compartment 24 b.
[0024] Referring briefly to both FIGS. 5 and 6 , the interior cross-section of the supply-conduit 30 a , 30 b may vary inversely with the distance between the cross-section and the fluid supply at the output port 38 a , 38 b of the controller 34 a , 34 b as measured along the longitudinal axis of the supply-conduit 30 a , 30 b . This decreasing interior cross-section at portions of the supply-conduit 30 a , 30 b remote from the controller 34 a , 34 b helps to make the pressure of fluid within the supply-conduit 30 a , 30 b more uniform throughout its length.
[0025] Referring now to FIG. 7 , a cargo container according to a fourth embodiment of the invention is generally illustrated at 10 c . In this embodiment, the supply-conduit 30 c is an independent assembly separate from the structure of the cargo container 10 c . The supply-conduit 30 c may be attached to the cargo container 10 c , and as illustrated is attached to the lateral portion 28 c of the cargo compartment 24 c.
[0026] Referring briefly now to FIGS. 2 and 7 , it can be observed that the supply conduit 30 , 30 c in the first and fourth embodiments is substantially within the cargo compartment 24 , 24 c.
[0027] Referring now to FIG. 8 , a cargo container according to a fifth embodiment of the invention is generally illustrated at 10 d . Just as in the first embodiment of the cargo container 10 , the supply-conduit 30 d is formed integrally from the structure of the cargo container 10 d , and more particularly is illustrated as an integral portion of the first side assembly 16 d . However, in the case of the fifth embodiment, the supply-conduit 30 d is substantially outside the cargo compartment 24 d.
[0028] Referring finally now to FIG. 9 , a cargo container according to a sixth embodiment of the invention is generally illustrated at 10 e . Just as in the fourth embodiment of the cargo container 10 c , the supply-conduit 30 e is an independent assembly separate from the structure of the cargo container 10 c . However, while the supply-conduit 30 e may be attached to the cargo container 10 c , in this sixth embodiment it is substantially outside the cargo compartment 24 e.
[0029] 2. Operation
[0030] Referring now to FIGS. 1 through 9 , the operation of the six embodiments of the cargo container 10 , 10 a , 10 b , 10 c , 10 d , 10 e will now be described. Except when reference is being made specifically to an alternate feature of one of the alternate embodiments, the alphabetic suffixes will be omitted from all reference numbers for the purpose of simplicity.
[0031] With the door sub-assembly 26 placed in its open position, the cargo compartment 24 is made accessible for loading cargo. The corrugated floor 58 incorporated into the floor assembly 14 provides a robust surface for loading and securing the cargo and the corrugations help to carry any water that may accumulate within the cargo compartment 24 away from the cargo. Once the cargo has been loaded into the cargo compartment 24 , the door sub-assembly 26 is placed in its closed position to seal the cargo compartment 24 .
[0032] Either during loading or after the cargo compartment 24 has been sealed, an operator can set the controller 34 to urge an environmental component of the fluid supplied at the output port 38 toward a desired value, for example a desired temperature or humidity. The operator can also engage the pump or fan 56 to provide motive force to circulate the fluid through the controller 34 to the supply-conduit 30 , on through the vent 32 into the cargo compartment 24 , and then back through the return-conduit 50 to the controller 34 .
[0033] With the supply-conduit 30 , the vent 32 , and the return-conduit 50 being oriented as previously described, the fluid flow through the cargo compartment 24 has a significant horizontal component, as is advantageously found in warehouse facilities.
[0034] While specific embodiments of the invention have been described and illustrated, such embodiments should be considered illustrative of the invention only. | A method and apparatus for controlling the environment of cargo through lateral ventilation. The method provides for a controlled fluid to be supplied into a cargo compartment having a lateral portion, the fluid being supplied through a vent in a supply-conduit adjacent the lateral portion. In practice, this result can be achieved by building a structure that encloses a cargo compartment having a lateral portion, running a supply-conduit adjacent the lateral portion, connecting the supply-conduit to receive a controlled fluid from outside the cargo compartment, and conducting the fluid into the cargo compartment through a vent in the supply-conduit. On mixing with the environment within the cargo compartment, the fluid will influence components of the environment, for example the humidity and the temperature. | 5 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a process for manufacturing an IC card. More particularly, the present invention relates to a process for manufacturing an IC card having a plane coil in which a conductor line is wound a plurality of times on substantially the same plane, and terminals of the plane coil and electrode terminals of a semiconductor element are electrically connected to each other.
[0003] 2. Description of the Related Art
[0004] As shown in FIG. 15, an IC card is composed of a rectangular plane coil 100 , in which a conductor 102 is wound a plurality of times, and a semiconductor element 104 . The above plane coil 100 and semiconductor element 104 are disposed between two sheets of resin films 106 made of PVC, on the surfaces of which characters are printed. These two sheets of resin films are bonded to each other by an adhesive layer made of polyurethane resin. The plane coil 100 and semiconductor element 104 are sealed by the adhesive layer.
[0005] When the thus formed IC card passes through a magnetic field formed in a card processor, electric power is generated by electromagnetic induction caused in the plane coil 100 of the IC card. Therefore, the semiconductor element 104 is started by electric power generated by electromagnetic induction, so that communication can be made between the semiconductor element 104 of the IC card and the card processor via the plane coil 100 which functions as an antenna.
[0006] Concerning the conventional plane coil 100 incorporated into the IC card, there is provided a conventional plane coil formed in such a manner that a covered electric wire is wound a plurality of times.
[0007] However, when the plane coil 100 is formed by winding the covered electric wire, it is difficult to reduce the manufacturing cost of the plane coil 100 . Also, it is difficult to efficiently mass-produce the IC cards. As a result, it is difficult to promote the spread of the IC cards.
[0008] In order to solve the above problems, Japanese Unexamined Patent Publication No. 6-310324 discloses a method of forming a plane coil by means of punching.
[0009] As disclosed in the above patent publication, when the plane coil is formed by means of punching, it becomes possible to reduce the cost of the IC card and also it is possible to mass-produce it compared with a conventional IC card, the plane coil of which is made by winding a covered electric wire.
[0010] However, it was found that the handling property of the above plane coil formed by means of punching is very low. When no forces are given to the rectangular plane coil 100 , which has been formed by punching, from the outside, predetermined intervals are formed between the conductor lines 102 adjacent to each other in the peripheral direction as shown in FIG. 16( a ).
[0011] However, when external force F is given to the plane coil 100 in the traverse direction as shown in FIG. 16( b ), the conductor line 102 is deformed, and short circuits occur when the adjacent conductor lines 102 come into contact with each other.
[0012] The above contact of the conductor lines 102 is caused by deformation of the conductor lines 102 themselves, as follows. In the process of manufacturing the IC card, for example, when an external force is given to the plane coil 100 for conveying and accommodating it, the conductor lines 102 are deformed. Also, when the plane coil 100 is disposed between the resin films 106 , on one side of which an adhesive layer is provided, an external force generated by a flow of the adhesive is given to the conductor line 102 in the traverse direction, so that the conductor lines 102 are deformed.
[0013] Therefore, it is an object of the present invention to provide a method of manufacturing an IC card in which short circuit is seldom caused by deformation of the conductor lines generated by an external force given to the plane coil in the traverse direction when the plane coil is conveyed and accommodated in the process of manufacturing the IC card.
SUMMARY OF THE INVENTION
[0014] The present inventors made investigation to solve the above problems. As a result, they accomplished the following invention as follows. A tape member is made to adhere to a plurality of portions of the plane coil 100 , so that the conductor lines 102 composing the plane coil 100 are kept in such a manner that the respective conductor lines 102 are arranged at predetermined intervals with respect to the adjacent conductor lines 102 . Due to the above arrangement of the conductor lines 102 , when the plane coil 100 is conveyed and accommodated, it is possible to prevent the occurrence of short circuit caused by deformation of the conductor lines 102 .
[0015] According to the present invention, there is provided a process for manufacturing an IC card comprising the following steps of: forming a plane coil by etching or punching a thin metal plate so that the plane coil consists of a conductor line wound as several loops in substantially the same plane and has respective terminals; mounting a semiconductor element on the plane coil, the semiconductor element having electrodes, and attaching an adhesive agent or tape to a predetermined area of the plane coil so that adjacent conductor lines in the loops are kept a predetermined gap therebetween; and inserting the plane coil between a pair of films to cover the plane coil therebetween, at least one of the films being provided with adhesive layer on a surface facing to the other film to seal the plane coil with the semiconductor element by attaching the pair of films with respect to each other by means of the adhesive layer.
[0016] The process further comprises a following steps of: electrically connecting to the electrodes of the semiconductor element to the respective terminals of the plane coil, after the semiconductor element is mounted on the plane coil and before the plane coil is sealed by the pair of films.
[0017] The process further comprises the following steps of: forming an IC card frame by etching or punching a thin metal plate so that the IC card frame comprises at least one plane coil consisting of a conductor line wound as several loops in substantially the same plane and having respective terminals and a frame connected to and spaced by a predetermined distance from the plane coil so as to support the plane coil; and separating the plane coil from the frame.
[0018] The separating step comprises a step of: separating individual plane coil from the frame; thereafter the individual plane coil is sealed with the semiconductor element by means of the pair of films.
[0019] The plurality of individual plane coils are continuously sealed by means of the pair of films; thereafter the films are cut and separated to obtain individual IC cards.
[0020] The process further comprises the following steps of: forming an IC card frame comprising at least one plane coil, at least one inner frame portion and an outer frame portion, the inner and outer frame portions are located inside and outside of the plane coil and connected to and spaced by a predetermined distance from innermost and outermost conductor lines of the plane coil so as to support the plane coil; and separating the plane coil from the inner and outer frame portions.
[0021] The process further comprises the following steps of: separating the inner frame portion from the innermost conductor lines of the plane coil, after the adhesive agent or tape is attached to the plane coil; and separating the outer frame portion from the outermost conductor lines of the plane coil, after the plane coil is sealed with the semiconductor element by means of the pair of films.
[0022] The process further comprises following steps of: forming an IC card frame by etching or punching a thin metal strip so that the IC card frame comprises a plurality of plane coils continuously arranged in a longitudinal direction of the thin metal strip, each plane coil consisting of a conductor line wound as several loops in substantially the same plane and having respective terminals, a plurality of inner frame portions each located inside an innermost conductor line of the respective plane coil and an outer frame portion located outside outermost conductor lines of the plane coils, the inner and outer frame portions are connected to and spaced by a predetermined distance from innermost and outermost conductor lines of the plane coil so as to support the plane coils; mounting semiconductor elements on the respective plane coils, each semiconductor element having electrodes, and attaching an adhesive agent or tape to a predetermined area of the respective plane coil so that adjacent conductor lines in the loops are kept a predetermined gap therebetween; and separating the individual plane coils from the inner and outer frame portions.
[0023] The plane coil forming step comprises: forming a bent portion protruded outward or inward from conductor lines in the respective loops of the plane coil.
[0024] The plane coil forming step comprises forming connecting pieces for connecting adjacent conductor lines in the loops of the plane coil to keep a predetermined gap between the adjacent conductor lines; and removing the connecting pieces after the steps of attaching an adhesive agent or tape to the plane coil.
[0025] According to another aspect of the present invention, there is provided a process for manufacturing an IC card comprising the following steps of:
[0026] forming an IC card frame by etching or punching a thin metal strip so that the IC card frame comprises a plurality of plane coils continuously arranged in a longitudinal direction of the thin metal strip, each plane coil consisting of a conductor line wound as several loops in substantially the same plane and having respective terminals, a plurality of inner frame portions each located inside an innermost conductor line of the respective plane coil and an outer frame portion located outside outermost conductor lines of the plane coils, the inner and outer frame portions being connected to and spaced by a predetermined distance from innermost and outermost conductor lines of the plane coil so as to support the plane coils;
[0027] mounting semiconductor elements on the respective plane coils, the each semiconductor element having electrodes, and attaching an adhesive agent or tape to a predetermined area of the respective plane coil so that adjacent conductor lines in the loops are kept a predetermined gap therebetween; and
[0028] separating the respective inner frame portions from the respective innermost conductor lines of the respective plane coils of the IC card frame, and thereafter
[0029] inserting the IC card frame between a pair of films to cover the respective plane coils therebetween, at least one of the films being provided with adhesive layer on a surface facing to the other film to seal the plane coils with the semiconductor element by attaching the pair of films with respect to each other by means of the adhesive layer; and
[0030] separating the outer frame portion from the respective outermost conductor lines of the respective plane coils to obtain an individual IC card.
[0031] According to the present invention as mentioned above, when an adhesive member and/or tape member is made to adhere to a predetermined portion of the plane coil formed by the etching or punching of a metallic sheet, it is possible to maintain the state of the conductor lines of the plane coil which are wound at predetermined intervals with respect to the adjacent conductor lines. Due to the above arrangement, when the plane coil is conveyed, even if an external force is given to each conductor line in the traverse direction, the conductor line is seldom deformed. Therefore, it is possible to prevent the occurrence of short circuit caused by the contact of the conductor lines with each other.
[0032] In order to prevent the deformation of conductor lines caused by conveyance until the adhesive member and/or tape member is made to adhere to a predetermined portion of the plane coil, it is preferable to form a frame for an IC card, to which the plane coil is partially connected, in the frame formed while a predetermined interval is left between the frame and the plane coil, wherein the frame for an IC card is formed by etching or punching a metal sheet.
[0033] When the respective conductor lines, which are adjacent to each other in the inside and the outside direction, are connected with each other by connecting pieces, the respective conductor lines, on the circumference composing the plane coil, can be integrated into one body. Therefore, deformation of the conductor lines can be further prevented.
BRIEF DESCRIPTION OF THE DRAWINGS
[0034] [0034]FIG. 1 is a process drawing showing an outline of a method of manufacturing an IC card of the present invention;
[0035] [0035]FIG. 2 is a plan view showing an embodiment of an IC card frame used in the present invention;
[0036] FIGS. 3 ( a ) and 3 ( b ) are partially enlarged plan views for explaining a bent portion of the plane coil shown in FIG. 2;
[0037] [0037]FIG. 4 is a plan view of a frame for an IC card showing a state in which a semiconductor element is incorporated into the plane coil shown in FIG. 2;
[0038] [0038]FIG. 5( a ) is a partially enlarged plan view for explaining a portion of the plane coil shown in FIG. 4 into which a semiconductor element is incorporated;
[0039] [0039]FIG. 5( b ) is a partially enlarged cross-sectional view for explaining a portion of the plane coil shown in FIG. 4 into which a semiconductor element is incorporated;
[0040] [0040]FIG. 6 is a plan view of a frame of an IC card showing a state in which a tape member is made to adhere to the plane coil shown in FIG. 4;
[0041] [0041]FIG. 7 is a plan view showing a plane coil separated from the frame for an IC card shown in FIG. 6;
[0042] [0042]FIG. 8 is a plan view showing a state in which the plane coil shown in FIG. 7 is disposed between two sheets of films;
[0043] [0043]FIG. 9 is a plan view showing a finally obtained IC card;
[0044] [0044]FIG. 10 is a plan view showing a state in which an inside frame is separated from the IC card frame shown in FIG. 6;
[0045] [0045]FIG. 11 is a plan view showing a state in which the frame for an IC card shown in FIG. 10 is disposed between two sheets of films;
[0046] FIGS. 12 ( a ) and 12 ( b ) are partially enlarged plan views for explaining another embodiment of a bent portion formed in the plane coil;
[0047] [0047]FIG. 13( a ) is a partially enlarged plan view for explaining another embodiment of a portion of the plane coil into which a semiconductor element is incorporated;
[0048] [0048]FIG. 13( b ) is a partially enlarged cross-sectional view for explaining another embodiment of a portion of the plane coil into which a semiconductor element is incorporated;
[0049] [0049]FIG. 14 is a partially enlarged cross-sectional view for explaining another embodiment of a portion of the plane coil into which a semiconductor element is incorporated;
[0050] [0050]FIG. 15 is a plan view for explaining a conventional IC card; and
[0051] FIGS. 16 ( a ) and 16 ( b ) are schematic illustrations for explaining a state in which an external force is given to a conductor line composing a conventional plane coil in the traverse direction.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0052] Some embodiments of the process for manufacturing an IC card of the present invention will be explained below by referring to the appended drawings.
[0053] [0053]FIG. 1 is a flow chart showing an embodiment of the process for manufacturing the IC card of the present invention. FIG. 2 is a view showing an embodiment of the IC card frame used in this flow chart. The frame 10 for the IC card shown in FIG. 2 is formed by etching or press-forming a metal sheet. There are provided an inside frame 14 and an outside frame 16 which are respectively formed inside and outside with a predetermined interval provided between them. The respective plane coils 12 , 12 are partially connected to the inside frame 14 and the outside frame 16 . The specific structure of the connection is described as follows. Support portions 18 , 18 . . . extending from a plurality of positions of the inner edge of the outside frame 16 are connected to the outermost conductor 2 a of the plane coil 12 . At the same time, support portions 20 , 20 . . . extending from a plurality of positions of the outer edge of the inside frame 16 are connected to the innermost conductor 2 b of the plane coil 12 .
[0054] When the plane coil 12 and the frame, which is formed with a predetermined interval provided between the outside and the inside frame, are partially connected to each other so that the plane coil 12 can b supported by the frame, the handling property of the plane coil 12 can be enhanced when it is conveyed and accommodated.
[0055] Examples of the metal sheets to be etched or press-formed are metal sheets made of copper, iron, aluminum and alloys of them. Especially when a metal sheet made of iron or aluminum is used, it is possible to reduce the manufacturing cost of the plane coil. In this connection, a metal sheet wound like a coil may be drawn out, so that it can be used as a metal sheet.
[0056] The plane coil 12 formed in the frame 10 used for the IC card shown in FIG. 2 is rectangular, and bent portions 22 , 22 . . . are formed in the straight line portions of the plane coil 12 . As shown in FIG. 3( a ), this bent portion 22 is formed in such a manner that a bent portion 24 protruding to the inside of the plane coil 12 is formed at the substantially same position of each conductor 2 composing the straight line portion of the plane coil 12 . Since the bent portions 22 are formed in the plane coil 12 , the rigidity can be enhanced. Due to the above structure, even if an external force is given to the plane coil 12 in the traverse direction when it is conveyed, deformation of the conductors 2 composing the plane coil 12 can be prevented. Therefore, the occurrence of short circuit caused by contact of the conductors with each other can be prevented.
[0057] Further, when the plane coil 12 is formed by punching a metal sheet, a punching clearance between the conductors composing the plane coil 12 becomes long and slender. Therefore, the rigidity of the punch is decreased. Due to the foregoing, there is a possibility that the punch is broken in the punching process and further the formed conductors are twisted. In order to solve such problems, when the bent portion 24 is formed in the conductor 2 on each circumference, a bent portion is also formed in the punch according to the configuration of the bent portion of the conductor 2 . Due to the foregoing, the rigidity of the punch can be enhanced. Accordingly, it is possible to prevent the punch from being damaged in the punching process, and also it is possible to prevent the occurrence of twist of the conductor 2 .
[0058] As shown in FIG. 3( b ), in the plane coil 12 shown in FIG. 2, there are provided a plurality of connecting pieces 26 for connecting the conductor lines 2 which are adjacent to each other in the inward and the outward direction of the plane coil 12 . By the above connecting pieces 26 , 26 . . . , the conductors 2 can be integrated into one body. Therefore, the conductors 2 are not collapsed. Due to the foregoing, when a plurality of frames 10 used for IC cards are laminated and conveyed or accommodated, the conductors 2 of the laminated plane coils are not entangled with each other. Therefore, deformation of the conductors 2 can be prevented.
[0059] When the above connecting pieces 26 , 26 . . . are formed stepwise between the conductors 2 as shown in FIG. 3( b ), the connecting pieces 26 , 26 . . . can be easily cut off by a punch for cutting as described later, and further it is possible to enhance the mechanical strength of the punch for cutting. That is, the connecting pieces 26 , 26 . . . are usually cut off all at once. Therefore, when the connecting pieces 26 , 26 . . . are formed in a straight line, the punch used for cutting becomes comb-shaped, and it becomes difficult to machine the punch used for cutting, and further the mechanical strength of the punch is decreased. From this viewpoint, when the connecting pieces 26 , 26 . . . are formed stepwise as shown in FIG. 3( b ), a position at which each punch for cutting is formed can be shifted according to the position at which each connecting piece 26 is formed. Accordingly, the punch for cutting can be easily machined, and the mechanical strength of the punch for cutting can be enhanced.
[0060] In this connection, the connecting pieces 26 , 26 . . . are cut off until a sealing process described later is conducted in which the plane coil 12 is sealed so that a predetermined interval can be formed between the wound conductors 2 .
[0061] As shown in FIG. 1, a semiconductor element is mounted on the plane coil 12 of the frame 10 for the IC card shown in FIGS. 2 and 3. The plane coil 12 on which the semiconductor element is mounted is shown in FIG. 4. As shown in FIG. 5( a ), the semiconductor element 28 is mounted at a position close to terminals 32 , 32 of the plane coil 12 . In a portion close to the terminals 32 , 32 of the plane coil 12 , an interval between the conductors 2 adjacent to each other is smaller than that of other portions as shown in FIG. 4. In the conductor 2 on each circumference, the clearance of which is smaller than that of other portions, there is provided a recess 35 , which is directed downward, as shown in FIG. 5( b ).
[0062] The semiconductor element 28 is mounted so that a face on which the electrode terminal 30 of the semiconductor element 28 is formed can be directed onto the bottom surface side of the recess 35 . As shown in FIG. 5( a ), the electrode terminals 30 , 30 of the semiconductor element 28 are connected to the terminals 32 , 32 of the plane coil 12 by wires 34 , 34 .
[0063] The terminal 32 of the plane coil 12 connected to the semiconductor element 28 by the wire 34 is subjected to squeezing, so that the terminal area can be extended, and at the same time an end face of the terminal is made to be lower than the conductor 2 . Due to the above structure, the mounted semiconductor element 28 is not protruded from a face of the plane coil 12 and, when wire bonding is conducted by the wedge bonding method, loops of the wires 34 , 34 do not protrude from the face of the plane coil 12 .
[0064] As shown in FIGS. 4 and 5, after the semiconductor element 28 has been mounted at a predetermined position of the plane coil 12 of the frame 10 for the IC card, an adhesive member and/or a tape member is bonded to the plane coil 12 as shown in FIG. 1. FIG. 6 is a view showing a state in which the tape member is bonded to the plane coil 12 . The tape members 36 are bonded to a plurality of positions of the plane coil 12 shown in FIG. 6. This tape member 36 is composed in such a manner that an adhesive layer is formed on one side of the tape member. In a portion to which this tape member is bonded, adhesive which has entered a space between the wound conductors is solidified, so that the conductors 2 can be fixed while a predetermined interval can be provided between them.
[0065] In the rectangular plane coil 12 shown in FIG. 6, when the tape member 36 is bonded to each straight line portion of the plane coil 12 , each conductor 2 composing the plane coil 12 can be fixed while a predetermined interval can be provided. Therefore, it is possible to cut off the connecting pieces 26 , 26 . . . for connecting the conductors of the plane coil 12 , and it is also possible to separate the plane coil 12 as shown in FIG. 1. This separation of the plane coil 12 is defined as follows. The plane coil 12 is separated from the inner frame 14 and the outer frame 16 of the frame 10 for the IC card.
[0066] As the tape member 36 for fixing the conductors 2 of the plane coil 12 , a hot melt sheet can also be used in place of the individual tape members 36 such as shown in FIG. 6. The hot melt sheet includes a hot melt adhesive provided on an exfoliation tape. The hot melt sheet is brought to be adhered to the plane coil 12 over the all area thereof from one side or respective sides thereof. Thereafter the connecting pieces 26 , 26 . . . of the plane coil 12 are cut off. The exfoliation tape of the hot melt sheet can be removed after the connecting pieces 26 , 26 . . . are cut off.
[0067] Otherwise, such a hot melt sheet may preferably be provided with openings at positions corresponding to the connecting pieces 26 , 26 . . . . The reason is that, since the connecting pieces 26 , 26 . . . are cut off by punching process after the exfoliation tape is removed from the hot melt sheet, it is necessary to prevent the hot melt adhesive from being adhered to the punch, when the punching operation is conducted from a side of the plane coil 12 to which the hot melt sheet is adhered.
[0068] As shown in FIG. 7, in the separated plane coil 12 , each conductor 2 is fixed by the tape member 36 . Therefore, even if an external force is given to the plane coil 12 in the traverse direction, each conductor 2 is not deformed. Accordingly, the occurrence of a short circuit caused by contact between the conductors can be prevented.
[0069] In this case, the tape member 36 is bonded to each straight line portion of the rectangular plane coil 12 . However, the tape member 36 may be bonded to each corner portion of the plane coil 12 , and also the tape member 36 may be bonded to both the straight line portion and the corner portion of the plane coil 12 . Instead of the tape member 36 , it is possible to use adhesive, and both the tape member 36 and the adhesive may be used together.
[0070] In this connection, the connecting portion 26 , 26 may be cut off after the plane coil 12 has been separated from the IC card frame 10 .
[0071] As described above, the plane coil 12 shown in FIG. 7 is separated from the IC card frame 10 , and the tape members 36 , 36 are bonded to the plane coil 12 and, further, the semiconductor element 28 is mounted on the plane coil 12 . As shown in FIG. 1, this plane coil 12 is disposed between two sheets of films and sealed by resin.
[0072] The plane coil 12 is sealed by resin as follows. As shown in FIG. 8, the tape members 36 , 36 , which have been separated from the frame 10 for the IC card, are bonded between two sheets of films 38 , 38 made of ABS resin or PET (polyethylene terephthalate) resin, at least on one of the opposing faces of which an adhesive layer is provided. When a plurality of plane coils 12 , 12 on which the semiconductor elements 28 are mounted are disposed between two sheets of films, the two sheets of films 38 , 38 are bonded to each other by the adhesive layer, and at the same time the plurality of plane coils 12 , 12 on which the semiconductor elements 28 are mounted can be sealed by resin.
[0073] In the above sealing process, each conductor 2 of the plane coil 12 is given a force in the traverse direction by a flow of adhesive. However, each conductor 2 on the circumference is fixed by the tape member 36 . Therefore, each conductor 2 on the circumference is not deformed.
[0074] The plurality of plane coils 12 , 12 disposed between the two sheets of belt-shaped films 38 , 38 are made into IC cards as shown in FIG. 1. In the process of making the plurality of plane coils 12 , 12 into IC cards, the films 38 , 38 joined by the adhesive layer are cut off at predetermined positions so that they can be made into individual bodies. In this way, the IC card shown in FIG. 9 can be obtained.
[0075] In this connection, faces of the two films 38 , 38 , which are opposite to the opposing faces, become surfaces of the finally obtained IC card. Therefore, various printing can be conducted on the faces.
[0076] The method of manufacturing the IC card, in which the plane coil 12 , to which the tape members 36 , 36 are bonded and the semiconductor element 28 is mounted, is separated from the frame 10 for the IC card and disposed between the two films is explained above. However, it is possible to adopt a method of manufacturing the IC card without separating the plane coil 12 from the frame 10 for the IC card. When the IC card is manufactured without separating the plane coil 12 from the frame 10 for the IC card, it is possible to reduce the number of processes in which the plane coil 12 separated from the frame 10 for the IC card is individually handled. Accordingly, the handling property of the plane coil 12 can be enhanced, and the IC card can be easily manufactured.
[0077] In the above method of manufacturing the IC card, as shown in FIG. 1, an adhesive member and/or a tape member is bonded to the plane coil of the frame for the IC card, and then a semiconductor element is mounted on the plane coil. After that, the inner frame is cut off. In the process of cutting off the inner frame, in the inner frame 14 and the outer frame 16 composing the frame 10 for the IC card shown in FIG. 6, the inner frame 14 is cut off, that is, in the inner frame 14 and the outer frame 16 which are partially connected to the inside and the outside of the plane coil 12 to which the tape member is bonded and on which the semiconductor element 28 is mounted, the inner frame 14 is cut off.
[0078] [0078]FIG. 10 is a view showing a frame 10 for the IC card in which the inner frame 14 is cut off. In the frame 10 for the IC card shown in FIG. 10, the plane coil 12 to which the tape member 36 is bonded and on which the semiconductor element 28 is mounted is supported by the support portions 18 , 18 . . . extended from the outer frame 16 under the condition that a large space 42 is formed inside the plane coil 12 .
[0079] At this time, the connecting pieces 26 , 26 . . . for connecting the conductors of the plane coil 12 are cut off. The connecting pieces 26 , 26 . . . may be cut off simultaneously when the inner coil 12 is cut off or before or after the inner coil 12 is cut off.
[0080] In this connection, when the frame 10 for the IC card, in which the large space 42 is formed inside the plane coil 12 as shown in FIG. 10, is conveyed to the punching process, other frame 10 for the IC card may enter the space 42 , or a metallic die for punching may be caught at the space 42 . Accordingly, there is a possibility that the handling property of the frame 10 for the IC card is a little lowered.
[0081] Therefore, when the plane coil 12 of the frame 10 for the IC card is disposed between two sheets of films as shown in FIG. 1, it is possible to cover the space 42 with the two sheets of films. As a result, the handling property of the frame 10 for the IC card can be enhanced.
[0082] The plane coil 12 of the frame 10 for the IC card disposed between the two sheets of films is shown in FIG. 11.
[0083] Two sheets of films 38 , 38 shown in FIG. 11 are belt-shaped films 38 , 38 made of resin such as ABS resin. The plane coils 12 , 12 on which the semiconductor elements 28 are mounted and a portion of the outer frame 16 are disposed between the two sheets of films 38 , 38 . An adhesive layer is provided on at least one of the opposing faces of the two films 38 , 38 which are opposed to each other. The two sheets of films 38 , 38 are joined to each other by this adhesive layer and, at the same time, the plane coils 12 , 12 on which the semiconductor elements 28 are mounted are sealed by the adhesive layer.
[0084] Next, the thus joined two sheets of films 38 , 38 are cut off at a predetermined position. At the same time, support portions 18 extending from a plurality of positions of the inner edge of the outer frame 16 are cut off. In this way, the plane coils 12 , 12 on which the semiconductor elements 28 are mounted are individualized. In this way, the IC card 40 shown in FIG. 9 can be provided.
[0085] It is preferable to determine the width of this film 38 so that the film 38 can sufficiently cover an overall face of the plane coil 12 and so that the film 38 can not close positioning holes 44 , 44 . . . formed in the outer frame 16 . The reason why the film 38 can not close positioning holes 44 , 44 . . . formed in the outer frame 16 is that the positioning holes 44 , 44 . . . are necessary when the outer frame 16 is cut off.
[0086] In this connection, the faces of the two films 38 , 38 , which are opposite to the opposing faces, become surfaces of the finally obtained IC card. Therefore, various printing can be conducted on the faces.
[0087] In FIGS. 7 and 11, the connecting pieces 26 are removed from the plane coil 12 disposed between the two sheets of films 38 , 38 . However, after the plane coil 12 has been disposed between the two sheets of films 38 , 38 , the connecting pieces 26 may be removed from the plane coil 12 . However, holes are formed on the films 38 , 38 at positions from which the connecting pieces 26 were removed. Accordingly, it is preferable that decoration films (not shown) are joined onto the films 38 , 38 .
[0088] The bent portion 22 of the plane coil 12 shown in FIGS. 1 to 11 is formed into a bent portion 24 in which the conductors 2 wound on the circumference are protruded in the same direction at the substantially same position as shown in FIG. 3( a ). However, the conductors 2 may be bent in such a manner that the bending directions of the conductors 2 in the bent portions 24 , 24 . . . are opposite to each other as shown in FIGS. 12 ( a ) and 12 ( b ). Further, positions at which the bent portions 24 , 24 . . . are formed may be different from each other as shown in FIG. 12( b ).
[0089] In the plane coil 12 described above, one bent portion 22 is formed in one straight line portion. However, a plurality of bent portions 22 may be formed in one straight line portion, that is, a plurality of bent portions 24 may be formed in the conductor lines 2 composing one straight line portion.
[0090] As shown in FIG. 13( a ), the plane coil 12 may be mounted on the face opposite to the face on which the electrode terminals 30 , 30 . . . of the semiconductor element 28 are provided, so that the conductors 2 of the plane coil 12 can pass on the face. In this case, as shown in FIG. 13( b ), a recess 35 directed upward is formed in a portion of each conductor 2 on which the semiconductor element 28 is mounted, and the semiconductor element 28 is mounted on the bottom face side of the recess 35 .
[0091] When the recess 35 is formed in each conductor 2 wound on the circumference as shown in FIG. 13( b ), there is a possibility that a portion of the conductor 2 forming the bottom portion becomes too thin. In this case, the recess 35 may be formed in such a manner that a portion of the conductor 2 is bent as shown in FIG. 14.
[0092] The frame 10 for the IC card described above is a belt-shaped frame for the IC card in which a plurality of plane coils 12 , 12 are formed, however, it is possible to use a frame for the IC card in which only one plane coil 12 is formed. In this case, concerning the two sheets of films 38 , 38 , it is necessary to use sheets of films suitable for the frame for the IC card in which one plane coil 14 is formed.
[0093] Instead of an arrangement in which the plane coil 12 , on which the semiconductor element 28 is mounted, is disposed between the two sheets of films 38 , 38 and the plane coil 12 is sealed by the adhesive layer formed on one side of the opposing faces, it is possible to adopt an arrangement in which the plane coil 12 , on which the semiconductor element 28 is mounted, is disposed between sheets of prepreg, and then films made of resin such as ABS resin are stuck on surfaces of the sheets of prepreg and heated so that the plane coil 12 can be sealed.
[0094] In this connection, in the explanations of FIGS. 1 to 14 , after the adhesive member and/or the tape member has been bonded to the plane coil on which the semiconductor element is mounted, the connecting pieces for connecting the conductors adjacent to each other in the inward and outward direction of the plane coil are cut off. However, the following procedure may be adopted. First, the adhesive member and/or the tape member is bonded to the plane coil, and then the connecting pieces for connecting the conductors adjacent to each other in the inward and outward direction of the plane coil are cut off. After that, the semiconductor element is mounted on the plane coil.
[0095] According to the present invention, in the process of manufacturing IC cards, it is possible to effectively prevent the deformation of the conductors composing the plane coil. Therefore, it is possible to prevent the occurrence of a short circuit which is caused when the conductors are contacted with each other due to deformation. As a result, the reliability of the IC card can be enhanced and the inspection of the IC card can be simplified. | A process for manufacturing an IC card includes a step of forming a plane coil by etching or punching a thin metal plate so that the plane coil consists of a conductor line wound as several loops in substantially the same plane and has respective terminals. A semiconductor element having electrodes is mounted on the plane coil. An adhesive agent or tape is attached to a predetermined area of the plane coil so that adjacent conductor lines in the loops are kept a predetermined gap therebetween. The plane coil is disposed between a pair of films to cover the plane coil therebetween, one of the films being provided with adhesive layer on a surface facing to the other film to seal the plane coil with the semiconductor element by attaching the pair of films with respect to each other by means of the adhesive layer. | 7 |
CROSS-REFERENCED TO RELATED APPLICATIONS
The present invention is related to U.S. Pat. No. 4,291,855 and to co-pending U.S. patent application Ser. No. 859,332 filed May 5, 1986, by C. S. Hungerford, Jr.
BACKGROUND OF THE INVENTION
The present invention relates to pipe or conduit saddles or clamps and in particular, to a saddle or clamp which is designed to be connected to a wooden joist or other frame members.
SUMMARY OF THE INVENTION
It is a principal object of the present invention to provide a pipe clamp or pipe saddle which is adapted to be secured to a wooden joist or other frame member.
A further feature of the invention is the provision of a pipe clamp having special structure facilitating the reception of fastener means for securing the clamp to a frame member.
A still further feature is the provision of a clamp device of the type disclosed in said '855 patent which includes at least one post found integrally with the clamp for receiving a fastener operative to connect the clamp to a frame member.
A further feature of the invention is the provision of a bore formed in the post leading to a guide means for maintaining proper alignment of a fastener driven through the bore into a frame member.
A clamp device embracing certain principles of the present invention may comprise a body including an integrally formed post element, a pair of arcuate, interlocking straps hinged individually to the body, and a bore formed in the post element for receiving a fastener for connecting the clamp device to the frame member.
Other features and advantages of the present invention will become more apparent from our examination of the succeeding specification when read in conjunction with the appended drawings in which:
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is a representation of a prior art pipe clamp connected to a metallic channel.
FIG. 2 is a side elevation of the clamp of the present invention shown secured to a wooden frame member.
FIG. 3 is a left side view of the illustration of FIG. 2 with parts broken away for clarity.
DETAILED DESCRIPTION OF PRIOR ART DEVICE OF FIG. 1
The clamp device of FIG. 1 is similar to the units disclosed and described in U.S. Pat. No. 4,291,855 and in copending U.S. patent application Ser. No. 859,332, filed May 5, 1986, entitled "A Connector Device for Supporting a Conduit in a Flange Channel", by C. S. Hungerford, Jr., in which a saddle or clamp 10 having releasable straps 11, supporting a pipe 12 is secured to a connector 13 by a screw 14. The connector 13 in turn engages the return bends or flanges 16 of a classic metal channel 17 to complete the connection.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring to FIGS. 2 and 3, a clamp device indicated generally at 18 includes interlocking straps 19 and 21 hinged to a clamp body 22 at 23 and 24, respectively.
The body 22 includes posts 26 and 27 having bores 28 and 29 (first guide means) for receiving a fastener such as a nail 31.
The body also includes spaced recesses or voids 32 and 33 portions of which define a V-shaped configuration in cross-section.
The bores 28 and 29 intersect the respective voids 32 and 33 at the apices 30 of the V-shaped configuration.
One sidewall 34 of each void defines a guide means (second guide means) in the forum of a flat planar surface which is tangent to the mating bore.
In effect, the guide means is an extension of a portion of the wall of the adjacent bore.
Thus, a nail received in the bore 28, for example, is guided along sidewall 34 facilitating entry of the nail into frame member 36.
While two posts 26 and 27 are shown it is entirely wherein the spirit and scope of the invention to fabricate the clamp device with a single post. One post is fully operative but two posts are desirable when the load is heavy. In addition, the posts preferably are provided with extensions 37 which allow for hammering of nail 31 without damage to hinges 23 and 24.
In all configurations, the clamp device is molded from suitable resinous material to generate a one piece unitary piece part.
It is to be understood that the invention is not limited to the illustrations described and shown herein, which are deemed to be merely illustrative of the best modes of carrying out the invention, and which are susceptible of modification of form, size, arrangement of parts and details of operation. The invention rather is intended to encompass all such modifications which are within its spirit and scope as defined by the claims. | A unitary device for supporting a pipe or other conduit operable to make a secure connection to a wooden joist or other frame member. | 5 |
BACKGROUND OF THE INVENTION
[0001] The invention relates to a multipole electrical switchgear apparatus, and in particular to a multipole switchgear apparatus comprising vacuum cartridges.
[0002] The document EP 0,346,603 describes a three-pole electrical switchgear apparatus comprising three identical polar breaking modules arranged side by side on a frame. Each module comprises a vacuum cartridge equipped with an operating rod movable in translation. A spring-loaded drive mechanism of known type comprising a pole shaft drives the operating rods of the three vacuum cartridges. Each operating rod is connected to the pole shaft by means of an independent connecting rod system proper to the corresponding breaking module. This connecting rod system is composed of a transmission lever arranged between two connecting rods, one of the connecting rods connecting the lever to a crank of the pole shaft and the other connecting rod connecting the lever to the operating rod of the vacuum cartridge. In practice, the vacuum cartridges of the different poles are liable to be subjected to different forces when either opening or closing takes place. When opening takes place, the contacts of a cartridge may be slightly welded, or on the contrary the electromagnetic forces induced by the currents on the contacts may tend to separate the contacts of one of the cartridges more violently. When closing takes place, in particular if it takes place on a short-circuit for one of the poles, one of the contacts may be subjected to very strong repulsion forces. On account of these different stresses on the rods of the vacuum cartridges of the different poles, the pole shaft is subjected to high torsion stresses, directly transmitted by the independent connecting rod systems of the different poles. There is then a risk of large dynamic torsional strain of the pole shaft, resulting in non-simultaneous closing or opening of the different cartridges. To counteract this risk, the pole shaft then has to be over-dimensioned so as to give it an additional torsional strength. Moreover, the switchgear apparatus does not enable the distance between the vacuum cartridges of the different poles to be easily varied. It is true that construction in identical and independent breaking modules would theoretically allow any arbitrary arrangement. However, a different pole shaft corresponds to each distance between poles, since the cranks of the pole shaft have to be spaced the same distance from one another as the cartridges. The pole shaft happens to be a particularly expensive part, all the more so as its torsional strength is critical. Furthermore, the necessity of providing different pole shafts for each distance between axes makes it impossible to design the mechanism as a functional unit pre-assembled in the plant independently from the breaking modules. The architecture hardly favors delayed differentiation of the different models of a switchgear apparatus range.
OBJECT OF THE INVENTION
[0003] One object of the invention is to achieve a multipole electrical switchgear apparatus with independent polar breaking modules enabling simultaneous operation of the different modules. Another objective is to increase the modularity of a multipole switchgear apparatus with independent polar breaking modules, enabling the distance between poles to be changed at low cost. Another objective is to obtain an architecture enabling standardized functional sub-assemblies to be stocked and assembled at the last moment to meet the customer's requirements.
[0004] According to the invention, these objectives are achieved by means of a multipole electrical switchgear apparatus comprising:
[0005] a support;
[0006] a drive mechanism equipped with a pole shaft rotating around a first geometric axis fixed with respect to the support;
[0007] a plurality of breaking modules, each module comprising:
[0008] a pair of separable contacts comprising at least one movable contact;
[0009] a movable rod securedly affixed to the movable contact;
[0010] a transmission lever pivoting around a second geometric axis parallel to the first geometric axis, said second geometric axis being common to all the breaking modules and fixed with respect to the support;
[0011] means for connecting the transmission lever to said rod;
[0012] comprising in addition a single connecting rod connecting the pole shaft to the transmission levers of the different breaking modules, the connecting rod being articulated on the one hand on at least two coaxial cranks of the pole shaft, defining a third geometric axis of pivoting parallel to the first geometric axis, and on the other hand on pivots ensuring pivoting of each transmission lever with respect to the connecting rod around a fourth geometric axis of pivoting parallel to the first geometric axis and common to all the breaking modules.
[0013] According to one embodiment, the movable rod is, in each module, connected to the connecting rod by means of a link pivoting around a fifth geometric axis parallel to the first geometric axis. A simple and advantageous geometric arrangement is thus obtained, ensuring a geometric transmission to a pole shaft situated at the height of the vacuum cartridges, while enabling the connecting rod to work in traction when closing of the contacts takes place. Preferably, the movable rod is connected to the connecting rod, in each module, by means of a link pivoting around a fifth geometric axis. The lever effect in this configuration enables the amplitude of the movement transmitted to be reduced and the forces to be geared down, which is particularly favorable when the contacts only have a small opening and closing travel, as is the case in particular for vacuum cartridges.
[0014] Preferably, the connecting rod is arranged so as to be solicited in traction when closing takes place. Closing is the sequence of movement where the forces transmitted by the connecting rod are the greatest. By making the connecting rod work in traction in this sequence, the strains on the connecting rod are limited. When opening takes place, the connecting rod is solicited in compression but the forces are relatively lower, so that the risks of deformation of the connecting rod out of its plane by buckling are avoided.
[0015] Preferably, the connecting rod comprises a metal plate shaped in such a way that its quadratic moment with respect to an axis perpendicular to a plane containing the third and fourth axes is high. The strength of the connecting rod in flexion in a plane containing the third and fourth axes enables any risk of delay on opening or closing of one of the pairs of contacts to be avoided.
[0016] According to a preferred embodiment, the connecting rod comprises a metal plate comprising two V-shaped arms, each V-shaped arm comprising a convergent end supporting a bearing for articulation with one of the cranks of the pole shaft, and a divergent end, the divergent ends of the two V-shaped arms being connected to one another by a base supporting bearings for articulation with the levers of the breaking modules.
[0017] According to one embodiment, the means for connecting the transmission lever to said movable rod comprise an insulating arm. This arrangement ensures insulation between the contacts and the mechanism which is accessible to operators.
[0018] According to one embodiment, the means for connecting the transmission lever to said movable rod comprise:
[0019] a contact pressure spring having two ends;
[0020] a first support means of a first end of the spring, securedly affixed to the lever;
[0021] a second support means of a second end of the spring, securedly affixed to the movable rod;
[0022] a mechanical connection between the first support means and the lever, performing full transmission of the movement of the lever in the closing direction and not performing transmission of the movement in the opening direction.
[0023] Preferably, each breaking module comprises a frame equipped with support bearings enabling pivoting of the transmission lever around the second axis of pivoting. The breaking modules can then be pre-assembled and tested in the plant before being assembled with the mechanism and connecting rod. This contributes to improving delayed differentiation.
[0024] Preferably, the connecting rod makes an angle close to a right angle with the transmission levers, and the movable rods work in translation in a plane appreciably parallel to the connecting rod. In other words, the geometric plane defined by the second and fourth geometric axes on the one hand and the geometric plane defined by the third and fourth geometric axes on the other hand make an angle of close to 90° between them, whereas the movable rod is parallel to the plane containing the third and fourth axes.
[0025] The invention is particularly well suited to a configuration wherein each breaking module comprises a vacuum cartridge forming an enclosure housing the separable contacts. However, it could be adapted to other breaking principles, provided that the opening and closing travel of the contacts is small.
BRIEF DESCRIPTION OF THE DRAWINGS
[0026] Other advantages and features will become more clearly apparent from the following description of a particular embodiment of the invention, given for non-restrictive example purposes only and represented in the accompanying drawings in which:
[0027] [0027]FIG. 1 represents an exploded view of a switchgear apparatus according to an embodiment of the invention, showing in particular a drive mechanism and breaking modules;
[0028] [0028]FIG. 2 represents a cross-sectional view of the switchgear apparatus of FIG. 1, in the open position;
[0029] [0029]FIG. 3 represents a perspective view of a kinematic transmission system connecting the mechanism to the breaking modules;
[0030] [0030]FIG. 4 represents a side view of the kinematic system, in the closed position.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0031] With reference to FIGS. 1 and 2, a three-pole switchgear apparatus 10 comprises a drive mechanism 12 and three identical breaking modules 14 , 16 , 18 , arranged side by side on the same side of a partition 20 separating the modules from the drive mechanism 12 . The partition 20 is formed by a metal plate having three windows 22 , 24 , 26 and is supported by a second metal plate 28 forming a bracket and acting as support base. The partition 20 is at earth potential and performs electrical protection of people.
[0032] The drive mechanism 12 can be of any known type comprising a pole shaft. It can for example be a mechanism of the type described in the document EP-A-0,222,645, equipped with a loading and closing sub-assembly comprising a closing spring, and with an opening sub-assembly comprising an opening spring. The essential thing with respect to the present invention is that the mechanism comprises an output shaft, which can also be called pole shaft. In the embodiment, the mechanism 12 is fixed to a support frame 30 and equipped with a pole shaft 32 supported by bearings 34 fixed to the frame 30 . The frame is itself fixed to the partition 20 .
[0033] As illustrated in FIG. 3, the pole shaft 32 comprises two double cranks 36 , 38 which pass through the wall of the frame via apertures and enable articulation to be achieved between the pole shaft 32 and a transmission rod 40 . The transmission rod 40 is formed by a flat part forming two double V-shaped arms 42 , 44 , spaced apart from one another and joined at their divergent ends by a base 46 . Each V-shaped arm 42 , 44 supports, at its convergent end, a pair of flanges 50 , 52 provided with coaxial bores, forming bearings. The cranks 36 , 38 also comprise coaxial bores forming bearings, so that a pivoting link of the hinge type is obtained between the double cranks 36 , 38 of the pole shaft 32 and the transmission rod 40 by insertion of spindles 54 in the corresponding bores of the double cranks 36 , 38 and of the double flanges 50 , 52 . The base 46 supports three pairs of flanges 60 , 62 , 64 provided with coaxial bores, forming bearings. By insertion of spindles 66 , these flanges enable a hinge type link to be achieved with three double levers 70 , 72 , 74 belonging to the three polar modules 14 , 16 , 18 of the apparatus and passing through the windows 22 , 24 , 26 of the partition 20 .
[0034] As the three breaking modules are identical, only the module 18 will be described. As illustrated in FIG. 2, the module 18 comprises a vacuum cartridge 80 supported by a frame 82 . The frame 82 is fixed to the wall 20 and to the support base 28 , so that the frame 30 , the metal plates 20 , 28 and the frames 82 of the three poles together form a support assembly 83 for the other parts of the apparatus. Two connecting strips 84 , 86 , fixed to the frame 82 , are designed to electrically connect the cartridge 80 to a busbar (not represented). The generic expression ‘vacuum cartridge’ designates in this case a sub-assembly of known type comprising a cylindrical body 88 forming an enclosure wherein a relative vacuum prevails and which houses a pair of separable contacts 90 , 92 connected to the connecting strips 84 , 86 . The body 88 is itself divided into a central insulating section 94 made of insulating material, a first metallic end section constituting a first closing flange 96 , and a second metallic end section constituting a second closing flange 98 . The contact 92 is stationary and is connected to the second flange 98 . The other contact 90 forms an axial end of a rod 100 movable in translation along its axis and passing through the body 88 of the cartridge via an orifice of the flange 96 . A sealing bellows 102 brazed onto the rod 100 and onto the internal wall of the first flange 96 allows an axial movement of the rod 100 and of the movable contact 90 in translation with respect to the stationary contact 92 , while preserving the vacuum prevailing in the enclosure. Electrical connection of the rod 100 to the busbar is achieved by means of a flexible electrical connection 104 , one of the ends of this connection also constituting the connecting strip 84 .
[0035] Outside the enclosure, the rod 100 is connected to the double lever 74 by means of an insulating arm 110 . The insulating arm comprises a body made of plastic material 112 overmolding on the one hand the head of a first threaded rod 114 , and on the other hand the head of a second threaded rod 116 situated in the axial extension of the first rod 114 . The first threaded rod 114 is screwed into a tapped blind hole situated at the end of the rod 100 of the cartridge 80 . A tubular adjusting nut 118 is screwed onto the second threaded rod 116 . The nut 118 supports at one end a support seat 120 for one end of a contact pressure spring 122 . The other end of the spring 122 bears on a second support seat 124 , which rests on a bar 126 . The bar comprises a bore 128 forming a guide sheath through which the tubular nut 118 passes. The bar 126 rotates freely in the lateral spindles 130 supported by the arms of the lever 74 . The guide sheath 128 allows both translation of the nut 118 parallel to its axis and free rotation thereof. The nut 118 comprises a shoulder resting on the bar part 126 opposite the second support seat 124 . The two arms of the double lever 74 pivot around a spindle 132 supported by the frame 82 . The three breaking modules 14 , 16 , 18 of the apparatus 10 being arranged side by side, the pivoting spindles 132 of the levers 70 , 72 , 74 are aligned and parallel to the pole shaft 32 . The levers 70 , 72 , 74 are parallel.
[0036] The kinematic system connecting the pole shaft 32 to the rods 100 of the three breaking modules 14 , 16 , 18 thus comprises a single connecting rod 40 between the pole shaft 32 and the three double levers 70 , 72 , 74 of the breaking modules, and is extended in each module by an insulator 112 , one of whose ends slides in a sheath 128 rotating with respect to the double lever 70 , 72 , 74 , and the other of whose ends is secured to the rod 100 of the cartridge 80 . This kinematic system enables five geometric axes of parallel rotation to be defined: a first geometric axis 140 of pivoting of the pole shaft, a second geometric axis 142 of pivoting of the levers 70 , 72 , 74 , a third geometric axis 144 of pivoting of the connecting rod with respect to the cranks of the pole shaft, a fourth geometric axis 146 of pivoting of the connecting rod with respect to the levers, and a fifth geometric axis 148 of pivoting of the bars 126 with respect to the levers 70 , 72 , 74 . The first axis 140 and the second axis 142 are both fixed with respect to the support 83 , the other axes being mobile during the opening and closing sequences.
[0037] Strictly speaking, the movement imparted on the rod 100 of the cartridge 80 by this mechanism without any play between the moving parts would not be perfectly straight with respect to the frame 82 . However, the angle between the lever 70 , 72 , 74 and the rod 100 is always very close to a right angle, and the travel of the rod 100 of the cartridge between its open position and its closed position does not exceed a few millimeters, which corresponds to an angle of rotation of the lever not exceeding a few degrees, so that in the absence of play, the scope of radial movement of the rod 100 would be about one hundredth of its axial travel. In the embodiment described, this radial movement is absorbed by the clearances existing between the various elements of the kinematic system, in particular at the level of the spindles 130 , 132 . However, if a larger travel was desired, it would be possible to guide the bar 126 in an oblong of the lever 90 , 92 , 94 .
[0038] The kinematic system operates in the following manner. When the contacts are separated and the mechanism is open, the kinematic system is initially in the position represented in FIG. 2. When closing takes place, the closing spring of the mechanism 12 drives the pole shaft 32 counterclockwise over a travel of more than 50°. The connecting rod 40 transmits this movement uniformly to the three double levers 70 , 72 , 74 . In each of the breaking modules, the double lever pivots clockwise around the spindle 132 , driving the bar 126 which compresses the spring 122 by means of the support seat 124 . The closing force is then transmitted by the spring 122 to the movable contact 90 via the seat 120 , the nut 118 and the insulating arm 110 . The kinematic system is then in the closed position of FIG. 4, the contacts being closed.
[0039] When opening takes place, the opening spring of the mechanism 12 drives the pole shaft clockwise over a travel of more than 50°. The connecting rod 40 transmits this movement uniformly to the three double levers 70 , 72 , 74 . In each of the breaking modules, the double lever pivots counterclockwise around the spindle 132 in FIG. 4, directly driving the bar 126 , the nut 118 , the insulating arm 110 and the rod 100 of the movable contact, until the open position of FIG. 2 is reached.
[0040] The single connecting rod 40 has a high quadratic moment with respect to an axis perpendicular to the geometric plane containing the axes of pivoting of the connecting rod with respect to the pole shaft and the double levers. Although the structure of the connecting rod has been lightened to reduce its weight, the base 46 keeps the required strength. In other words, the forces applied to the connecting rod in its plane are not liable to induce a notable flexion of the connecting rod. Consequently, the connecting rod 40 gives the kinematic system a great strength, so that even if the forces to be applied to the different cartridges are different, their movement will nevertheless be simultaneous. By construction, the pole shaft 32 itself has a very great torsional strength, so that the two hinges joining the connecting rod 40 to the pole shaft 32 can be spaced apart which contributes to increasing the strength of the kinematic system even further.
[0041] The connecting rod is manufactured by being cut out from a sheet metal plate. The levers are also made of metal plate. The electrical insulation is achieved in each breaking module by means of the insulating arms. It should be noted that the insulating part 112 of the arm is shaped as a skirt so as to achieve optimum insulation.
[0042] To modify the distance between the axes of the polar modules, the connecting rod and, if necessary, the wall 20 , which are very inexpensive parts, simply have to be changed. Each specific connecting rod has a base of a different length and especially flanges 60 , 62 , 64 of variable number and locations. The distance between the flanges 50 , 52 performing the hinge link with the cranks of the pole shaft on the other hand remains constant. The pole shaft 32 thus remains identical whatever the distance between the axes of the polar modules, which means that the mechanism 12 can be pre-assembled in the plant and forms a functional unit for the whole of the range. In like manner, the breaking modules 14 , 16 , 18 are identical whatever the distance between axes chosen. This enables assembly of the apparatus to be deferred until the customer has made his choice.
[0043] Various modifications are naturally possible. The number of modules is not limited to three: the invention applies equally to two-pole, four-pole, or even six-pole or eight-pole apparatuses. The levers 70 , 72 , 74 can be single. The drive mechanism can be of any type: with distinct closing and opening springs to enable a closing, loading, opening, closing, opening sequence; or with a single spring enabling closing and opening. | A multipole electrical switchgear apparatus comprises a drive mechanism equipped with a pole shaft and a plurality of breaking modules. Each module comprises a vacuum cartridge moved by a movable rod articulated on a transmission lever. The pole shaft is linked to the transmission levers by means of a connecting rod. This common connecting rod gives the kinematic transmission system a great strength. Furthermore, it enables switchgear apparatuses having variable distances between breaking modules to be produced inexpensively, based on a standard pole shaft. Finally, it enables differentiation of the switchgear apparatuses to be delayed. | 7 |
RELATION TO PRIOR APPLICATIONS
[0001] The present invention claims priority through U.S. Provisional Application No. 60/389,965, filed Jun. 19, 2002.
FIELD OF INVENTION
[0002] The present invention relates generally to the field of coronary medical devices. More specifically, the present invention discloses a coronary dialysis apparatus that is useful for providing therapies to treat atherosclerosis and related diseases.
BACKGROUND OF THE INVENTION
[0003] Every year about 1.5 million people in the United States have heart attacks, and more than half of them die. Vulnerable plaque as the major underlying cause of acute coronary syndromes and sudden cardiac death is now the focus of interest in cardiovascular medicine. The fast growing body of knowledge about atherosclerosis and the pressing need for early detection and treatment of patients at risk of fatal heart attacks has led to the emergence of the new field of “vulnerable plaque.” In the past several years, the field of vulnerable plaque research has evolved in a rapid and progressive way. As the understating of the culprit lesions is changing, terminologies and criteria for definitions and classifications need to be revised and updated.
[0004] Several kinds of clinical observations suggested that instead of progressive growth of the intimal lesion to a critical stenosis, complication of a not necessarily occlusive plaque by thrombosis most often causes episodes of acute coronary syndrome. It is now appreciated that physical disruption of the atherosclerotic plaque commonly causes acute thrombosis.
[0005] The two major modes of plaque disruption provoke most coronary thrombi. The first mechanism, accounting for some two thirds of acute coronary syndrome (“ACS”), involves the fracture of the plaque's fibrous cap. The second mode involves a superficial erosion of the intima.
[0006] Atherosclerosis, formerly considered a lipid storage disease, actually involves an ongoing inflammatory response. Substantial advances in basic and experimental science have illuminated the role of inflammation and the underlying cellular and molecular mechanisms that contribute to atherogenesis. Recent advances in basic science have established a fundamental role for inflammation in mediating all stages of this disease from initiation through progression and, ultimately, the thrombotic complications of atherosclerosis. These new findings provide important links between risk factors and the mechanisms of atherogenesis. Clinical studies have shown that this emerging biology of inflammation in atherosclerosis applies directly to human patients.
[0007] Current therapies include patient counseling, dietary counseling, pharmacotherapy, life style modification, and surgery. Even with aggressive thrombolytic, anticoagulant, and/or antiplatelet agents or interventional therapy, patients with ACS still have a 12% to 16% incidence of major cardiac events at 4 to 6 months after hospital discharge. Novel treatments based on increased understanding of the underlying mechanisms of plaque instability should yield further improvements in outcomes. Growing evidence indicates that in ACS, elevated circulating inflammatory markers, such as CRP, serum amyloid A, IL-6, and IL-1 receptor antagonist commonly accompany ACS. Such elevations correlate with in-hospital and short-term adverse prognosis and may reflect not only a high prevalence of myocardial necrosis, ischemia-reperfusion damage, or severe coronary atherosclerosis but also a primary inflammatory instigator of coronary instability in particular C-reactive protein (CRP) which predicts an unfavorable course, independent of the severity of the atherosclerotic or ischemic burden. Thus, inflammation represents one potential novel pathophysiological mechanism of the ACS that may furnish such a new target for therapy.
[0008] A large number of experimental studies have shown that augmentation of HDL and its apoprotein may have vascular protective, preventive, and therapeutic effects. Conventional treatment of patients suffering from acute coronary syndrome (ACS) consists typically of antiplatelet, anticoagulant, thrombolytic therapy, including percutaneous coronary intervention. Taking in to account the fact that there are at least 2-3 vulnerable plaques in each patient as well as inaccessibility of about 50% of lesions by stents, other strategies are important in stabilizing vulnerable plaques within the coronary circulation. One way a effect may be achieved is by delivering high dose of drugs that are able to stabilize the plaques. Additionally, harmful and other unwanted toxic substances that are involved in atherogenesis, plaque vulnerability, and acute coronary syndrome may be removed from the blood to decrease complications and recurrence rate of acute coronary syndromes as well as increasing the survival of the patients.
[0009] Typically, several dozen plaques are found in arteries afflicted by ACS disease. It is the rupture of these plaques that brings about the terminal stage of the disease. The rupture causes a large thrombus to form which may or may not completely occlude the vascular lumen. The importance of diffuse therapy would be clearer by understanding the inaccessibility of nearly 50% of coronary artery plaques by stent.
[0010] Cholesterol removal and excretion is at least as important as cholesterol mobilization from peripheral tissues. For example, implementation of any therapeutic strategy that could deliver high dose of HDL in to the target organ (coronary circulation) through systemic administration of drug could facilitate the process of plaque stabilization. On the other hand because HDL therapy may only mobilize the peripheral cholesterol through reverse cholesterol transport mechanism but may not be able to remove or excrete the cholesterol from the body. Current LDL aphaeresis machine using plasmaphaeresis and selective LDL aphaeresis is able to precipitate LDL and a limited number of plasma harmful factors but adding the other technique such as immunprecipitation, selective absorption, and filtration to the current LDL aphaeresis technology will increase the capabilities to decrease more harmful factor as possible. By combining the LDL aphaeresis machine together with a system that is able to deliver high dose of HDL to the circulation as well as coronary circulation, we would be able not only mobilizing the cholesterol from the peripheral tissues but also we are able to remove and facilitate the excretion of the effluxed cholesterol out of the body.
[0011] On the other hand by addition of other technique to the established LDL aphaeresis machine such as immunoprecipitation (immunoabsorption) and other precipitating mechanisms would be able to precipitate and filterate more harmful substances for patients with chronic coronary artery disease.
[0012] C-reactive protein (CRP) is a trace serum protein which elevates up to 1000-fold in concentration in association with inflammation and tissue necrosis. CRP binds with phosphocholine and phosphate esters; initiates reactions of agglutination, opsonization and complement consumption; and precipitates with protamine and synthetic polymers of lysine and arginine, and these reactivities are modulated by calcium and phosphocholine. There is report on the interactions of heparin with these polycations in the absence and presence of CRP, which show marked similarities to reactions between antigen and antibody. Heparin optimally precipitated with the polycations over a narrow range of reactant ratios, peaking at slight anion charge excess.
[0013] Clinical studies affirm correlation of circulating markers of inflammation such as CRP with propensity to develop ischemic events and with prognosis after ACS. Intralesional or extralesional inflammation may hasten atheroma evolution and precipitate acute events. Circulating acute-phase reactants elicited by inflammation may not only mark increased risk for vascular events, but in some cases may contribute to their pathogenesis. So it may be logical that decreasing the level of inflammatory markers such as CRP may have significant effect on the pathogenesis of atherosclerosis and its complication (ACS). This may be achieved by adding and combining specific chamber to the dialysis machine to precipitate CRP.
[0014] Human C-reactive protein is associated with lipids. Isolation of pure lipid-free C-reactive protein was obtained by a three step procedure. First, partially lipid-free C-reactive protein was obtained by affinity chromatography; second, lipid-bound proteins were eliminated by calcium-dependent precipitation; and third, lipid-free pure C-reactive protein was obtained by affinity re-chromatography of the supernatant-4 46-50% yield of lipid-free C-reactive protein was obtained compared with the 14.7% obtained by the old method of extraction with lipid solvents.
[0015] Febrile-range temperature induction in this invention relates to the treatment of the harmful inflammation and inflammatory mediators such as cytokines in the body tissue by exposing the inflammatory cells and blood to heat. A plaque is an accumulation of cholesterol, proliferating smooth muscle cells, and inflammatory cells covered by cellular secretion of collagen that formed the cap over the plaque in the vessel wall. Macrophages migrate in to and accumulate in the plaque causing inflammation which causes the plaque prone to rupture and formation of blood thrombus. Rupture typically is caused by inflammatory cells, primarily macrophages. These cells release enzymes that tend to degrade the cap. A number of studies have shown that heat may induce programmed cell death. Heating also causes the melting or de-crystallization of the cholesterol crystal within the plaque. So heating the blood (41-42° C.) within the machine during its passage is another plaque stabilizing method that implemented in this patent in order to decrease the inflammatory process within vulnerable atherosclerotic plaques. On the other side it has been shown that febrile range temperature by itself may modify the profile of plasma level of some cytokine such as TNF-alpha, IL-1, and IL-6 making it logical to speculate that heating the blood to the febrile range level may have some useful effect in reducing the level of some cytokine especially in acute coronary syndrome as well as stabilizing the vulnerable plaques.
[0016] In general, coronary dialysis system 1 may be used for separating harmful substances such as LDL, fibrinogen, C reactive protein, and cytokines from circulation. Coronary dialysis system 1 may deliver high level of HDL locally and maintain appropriate plasma level of HDL to reduce its unwanted side effects. This system is also capable of maintaining blood oxygenation, (even delivering hyperbaric oxygen to coronary artery system), sustaining appropriate coronary perfusion pressure and distributing blood with increased temperature.
[0017] Systemic coronary dialysis system is provided for performing dialysis of the blood of patients suffering from atherosclerosis in order to reduce the rate of the progression of atherosclerotic plaques, reducing the vulnerability of plaques by compositional changes in the plaque, and even inducing plaque regression. This system designed mainly on the basis of reducing coronary artery disease risk factors especially those which are resistant to the conventional therapeutic modalities or for those there has not been any proven and effective treatment, such LDL aphaeresis and adding the useful factors to the circulation which may have beneficial effect in plaque stabilization.
[0018] Systemic drug therapy has a problem of drug dilution that may decrease the effectiveness of the treatment and raise the issue of hazard systemic side effects. In contrast, local therapeutic modality and local drug and/or gene delivery would provide more effective treatment to affect the process of atherogenesis and stabilize atherosclerotic plaques.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] [0019]FIG. 1 is a schematic overview of an exemplary system;
[0020] [0020]FIG. 1A is a schematic overview of a multi-chambered dialysis machine in situations where the cardiac circulatory system is completely isolated from systemic circulation, e.g. by an inflatable balloon at the tip of the perfusion catheter so that oxygenation of the processed blood is required;
[0021] [0021]FIG. 1B is a schematic overview of a multi-chambered dialysis machine 100 in cases where the step of oxygenation is not required;
[0022] [0022]FIG. 2 is a plan view in partial cutaway of two perfusion or dialysis catheters within an arterial shield;
[0023] [0023]FIG. 3 is a plan view of two perfusion or dialysis catheters within a vehicle catheter;
[0024] [0024]FIG. 3 a is a cross section of a vehicle catheter exemplar showing two perfusion catheters disposed within as well as a pressure or vacuum channel;
[0025] [0025]FIG. 4 a is a cross section of a perfusion catheter showing a temperature channel, pressure channel, and inflation channel;
[0026] [0026]FIG. 4 b is a cross section of a perfusion catheter, collection catheter, or vehicle catheter with a balloon configuration to substantially occlude the vessel into which the catheter is placed;
[0027] [0027]FIG. 4 c is a cross section of a perfusion catheter, collection catheter, or vehicle catheter with a ring balloon configuration which will not completely occlude the vessel into which the catheter is placed;
[0028] [0028]FIG. 4 d is a cross section of a perfusion catheter, collection catheter, or vehicle catheter with a butterfly balloon configuration which will not completely occlude the vessel into which the catheter is placed;
[0029] [0029]FIG. 5 a is a schematic of a coronary system using femoral entry;
[0030] [0030]FIG. 5 b is a plan view in partial cutaway showing two perfusion catheters disposed through the aorta into two separate vessels;
[0031] [0031]FIG. 5 c is a partial perspective view of a collection catheter and arterial shield where the collection catheter is placed into a coronary sinus;
[0032] [0032]FIG. 6 a is similar to FIG. 5 a but illustrates use of an aortic ring balloon;
[0033] [0033]FIG. 6 b is a partial cutaway showing a vehicle catheter with an aortic root ring;
[0034] [0034]FIG. 6B illustrates cross sections from proximal toward distal end of a vehicle catheter with an aortic root ring;
[0035] [0035]FIG. 7 illustrates the pathways of perfusion catheters and collecting catheter inserted through the femoral artery and the left subclavian vein respectively;
[0036] [0036]FIG. 8 a illustrates the pathways of perfusion catheters and collecting catheter inserted through the femoral artery and femoral vein respectively;
[0037] [0037]FIG. 8 b illustrates the collection of blood in the right atrium by a collecting catheter introduced through the femoral vein;
[0038] [0038]FIG. 9 illustrates a non-coronary, systemic configuration; and
[0039] [0039]FIG. 10 illustrates a pericardial configuration.
DETAILED DESCRIPTION OF THE INVENTION
[0040] As used herein, “catheter” is either a general term as will be understood by those of ordinary skill in the medical arts or a specific type of catheter, as understood from the context.
[0041] Referring now to FIG. 1, coronary dialysis system 1 comprises multi-chambered dialysis machine 100 and catheter system 200 . Patient 10 is connected to coronary dialysis system 1 using catheter system 200 and blood routed through multi-chambered dialysis machine 100 to ameliorate blood components. The apparatus and methods disclosed and claimed herein may be used to deliver drugs, including continuous delivery of a high dose of drugs such as cholesterol removing drugs, locally into the coronary system of patient 1 . These may be used to stabilize vulnerable plaques, decrease the lipid content of the plaques, reduce inflammatory activity throughout the coronary system, change the cellular composition of the plaques by decreasing the macrophages and increasing the smooth muscle cells, and the like, or combinations thereof.
[0042] In addition to perfusion of doses, including high doses, of substances such as high density lipoprotein (HDL), gene therapy may be introduced directly to the coronary circulation using coronary dialysis system 1 . Harmful and/or unwanted plasma substances may be withdrawn from the circulation, e.g. by plasmaphaeresis and aphaeresis in which various separation methods such as precipitation, filtration, adsorption, and immunprecipitation (immunoabsorption). These harmful substances may include LDL, CRP, fibrinogen, LP(a), tissue factor, CD14, interleukin-1, interleukin-6, TG, plasminogen, complement components C3, C4, C 1 inhibitor, and the like, or combinations thereof. Warming the blood during its passage through multichambered dialysis machine 100 , e.g. using oxygenator 120 or heater 140 , by itself may reduce inflammatory process within the plaques, decrease the vulnerability of the plaques and decrease the level of some plasma cytokines such as TNF-alpha, IL-1, and IL-6. During processing, the homodynamic status of patient 10 may be under intensive control.
[0043] [0043]FIG. 1 a illustrates an exemplary configuration of multi-chambered dialysis machine 100 in situations where the cardiac circulatory system is to be completely isolated from systemic circulation, e.g. by use of inflatable balloon 222 (FIG. 2) at tip 221 (FIG. 2) of perfusion catheter 220 (FIG. 2). Such isolation requires oxygenation of the processed blood, e.g. via oxygenator 120 .
[0044] [0044]FIG. 1 b illustrates an exemplary configuration of multi-chambered dialysis machine 100 in cases where the step of oxygenation is not required.
[0045] Referring back to FIG. 1 a , multi-chambered coronary dialysis machine 100 comprises fluid inlet 102 , fluid outlet 104 , and a plurality of chambers 110 - 150 . Each chamber 110 - 150 may be designed for a specific purpose. Further, as used herein, each chamber 110 - 150 may be physically separate from at least one other chamber 110 - 150 , all other chambers 110 - 150 , or combined with one or more other chambers 110 - 150 . For example, heater 140 may be a separate chamber, included as part of oxygenator 120 , or both.
[0046] Referring back to FIG. 1, coronary dialysis system, 1 may be used to provide stabilization, including rapid stabilization, of vulnerable plaque. It may be appreciated that catheter system 200 (comprising perfusion catheter 220 (FIG. 2) and collecting catheter 210 (FIG. 5 a )) and multi-chambered dialysis machine 100 may be used to form a substantially closed circulatory pathway for a fluid such as a patient's blood. In an embodiment, blood is collected such as through collecting catheter 210 , drained through fluid inlet 102 (FIG. 1 a ) of multi-chambered dialysis machine 100 , and passed through several chambers 110 - 150 in which the blood may be filtered, precipitated, enriched, and pumped back through fluid outlet 104 (FIG. 1 b ) of multi-chambered dialysis machine 100 to the coronary circulation of patient 10 via perfusion catheter 220 .
[0047] Blood separation chamber 110 may be used to separate blood plasma from blood cells. Blood separation chamber 110 is in fluid communication with fluid inlet 102 (FIG. 1 a ) of multi-chambered dialysis machine 100 . It is understood that blood separation chamber 110 may comprise one or more chambers, e.g. plasmaphaerersis chamber 112 (FIG. 1 a ) and aphaeresis chamber 114 (FIG. 1 a ). Further, in an embodiment, blood separation chamber 110 comprises either a plasmaphaerersis (primary separation) chamber, an aphaeresis (plasma differential separation), or both, either as separation sub-chambers or as a single chamber.
[0048] Plasma may then be further processed by secondary and/or selective precipitation and filtration to remove undesired substances from the plasma, e.g. harmful and unwanted substances. These harmful and unwanted substances may include intrinsic particles like LDL, CRP, fibrinogen, or any added materials to the perfused blood such as high level of genes, drugs, and/or chelating agent. Blood separation chamber 110 may further comprise immune precipitation functionality to specifically precipitate and separate any plasma harmful factors to further decrease their plasma level.
[0049] In the blood separation chamber 110 , blood cells are temporarily separated from plasma. During aphaeresis of plasma components, LDL, CRP, fibrinogen, some plasma cytokines, chelating agents, and transgenic material may be separated such as through precipitation, filtration, and/or adsorption so that at the end of this stage of plasma processing, much toxic or harmful substances are removed from the plasma before it is admixed with its blood cells.
[0050] In an exemplary embodiment, oxygenator 120 comprises a gas exchanger in which the withdrawn deoxygenated venous blood is oxygenated to an appropriate level of oxygenation for use as natural arterial blood appropriate to be perfused directly into the coronary arterial system of patient 10 . Additionally, oxygenator 120 may further comprise heat exchanger 122 (FIG. 1 a ) as well as or in place of the gas exchanger. During the oxygenation process within oxygenator 120 , the blood temperature may be increased through heat exchanger 122 (FIG. 1 a ) to a desired level. Oxygenator 120 is necessary in cases where complete isolation of coronary circulation is desired.
[0051] Enricher 130 allows blood, e.g. in which oxygenated and detoxified blood, to be further processed. Processing in Enricher 130 may include including enrichment of blood with needed nutrients, drugs, including any high dosage level drugs, or other desired substances, e.g. those needed to stabilize an atherosclerotic plaque. Examples of substances needed to stabilize an atherosclerotic plaque and other therapeutic agents may include HDL or its main apoprotein (apoA-1), statins, chelating agents, genes, hyperbaric oxygen in case of acute coronary syndrome, or the like, or combinations thereof. Blood may also be enriched by adding therapeutic agents such as HDL, chelating agents, transgenes, and any drugs such as statin that may be delivered directly into the coronary circulation.
[0052] Heater 140 may be present to heat blood to a desired temperature, e.g. a therapeutic temperature of around 41-42° C.
[0053] Pump 150 allows fully processed blood to be pumped back to patient 10 with appropriate volume, perfusion pressure (flow), and appropriate temperature back into the isolated coronary arterial system of patient 10 .
[0054] In a preferred embodiment, chambers 110 - 150 are arranged in series with a predetermined sequencing. For example, chambers 110 - 150 may be configured to promote ameliorating of the blood sequentially, e.g. first cleaning harmful/unwanted materials from blood, then oxygenate the blood, then warm the blood, then enrich the blood with nutrients or drugs, and finally pump the blood back to the coronary system in this order to deliver, in a continuous fashion, a dose, including a high dose, of drugs in direct vicinity of coronary arteries and their endothelium an well as sub-endothelial layers.
[0055] Whether all or some of these chambers 110 - 150 are used may depend on the design of perfusing catheter 220 (FIG. 2) and collecting catheter 210 (FIG. 5 a ) used in a particular method. When complete isolation of coronary circulation is desired, it may be necessary to include blood separation chamber 110 , oxygenator 120 , enrichment chamber 130 , blood heating chamber 140 , and blood pump chamber 150 in multi-chambered dialysis machine 100 . In cases where complete isolation of coronary circulation is not established, oxygenator 120 may not be needed if sufficient arterial oxygenated blood flows into the coronary artery. Therefore only blood separation chamber 110 , enrichment chamber 120 , blood heating chamber 140 , and blood pump chamber 150 may be sufficient for blood processing and delivery in these latter cases.
[0056] In an embodiment, multi-chambered coronary dialysis machine 100 may comprise one or more microprocessors or other controllers (not shown in the figures) to aid in automatically providing for separation, treatment, and dialysis of blood with monitoring of the extracorporeal plasma circuit. Multi-chambered dialysis machine 100 may also be added to a hemodialysis machine to be used in patients suffering from chronic renal failure who are at high risk for atherosclerosis and its complications, e.g. diabetes mellitus patients.
[0057] Referring now to FIG. 2, catheter system 200 (FIG. 1) comprises a novel catheter system for either complete or incomplete isolation of the coronary circulatory system of patient 10 (FIG. 1) from systemic circulation, e.g. by means of ante grade perfusion catheter 220 introduced percutaneously from out of the body. Catheter system 200 acts as a delivery system for local introduction of processed blood directly into the coronary arteries.
[0058] Catheter system 200 (FIG. 1) may comprise several configurations designed to introduce processed blood by direct ante grade perfusion into the coronary arteries. For example, configurations may comprise presence or absence of vehicle catheter 230 (FIG. 3) for ante grade perfusion, presence or absence of inflatable balloon 232 (FIG. 3) at distal tip 231 (FIG. 3) of vehicle catheter 230 or inflatable balloon 222 at distal tip 221 of perfusion catheter 220 , and/or variation of inflatable balloon 222 for complete or incomplete isolation of the coronary circulation. 1
[0059] The coronary ostia may be occluded to substantially completely isolate coronary arteries from systemic circulation in order to prevent dilution of processed blood by the systemic blood. Consequently, high level of drug or therapeutic agent may be delivered to the intimate vicinity of coronary artery endothelial cells.
[0060] Alternatively, the coronary ostia may be left non-occluded so that the coronary artery system is perfused with processed blood as well as blood from the systemic circulation. By exposing endothelial cells to high level of local HDL, statin, genes, or chelating agents, it is anticipated that the present system would enhance the physiologic effects of these delivered therapeutic agents in lipid metabolism as well as plaque composition. As a result, lipid laden, high macrophage and low smooth muscle cell containing vulnerable plaques would undergo constitutional changes by decreasing lipid as well as macrophage content. When the plaques are stabilized in this way, plaque rupture and its consequences may be lessened if not prevented.
[0061] Referring now to FIG. 5 a , catheter system 200 may comprise arterial introducer 202 , collection catheter 210 , perfusion catheter 220 , and vehicle catheter 230 . As used herein, perfusion catheter 220 is equivalent to a perfusion dialysis catheter.
[0062] Arterial introducer 202 may be introduced through femoral artery 30 . Collecting catheter 210 may be introduced into coronary sinus ostium 27 (FIG. 5 c ) and completely occlude the ostium to collect and drain blood out of patient 10 for processing. Collecting catheter 210 may comprise multiple configurations, e.g. variations in catheter physical designation as well as differing configurations of balloon 212 (not shown in the figures).
[0063] Referring back to FIG. 2, FIG. 2 illustrates the design of a perfusion catheter 220 . Arterial sheath 202 is introduced through the femoral artery and comprises two or more ports through which one or more perfusion catheters 220 may be introduced and passed up to the coronary artery ostia. The distal end of perfusion catheter 220 has pre-shaped curvature so that it may be engaged into the coronary artery ostia readily. There is a lumen extending throughout either the entire length or a portion of perfusion catheter 220 through which the processed blood may be perfused to the coronary circulation. The lumen of perfusion catheter 220 is connected to the outlet of the dialysis machine. An inflation channel may also exist within or proximate the wall of perfusion catheter 220 for balloon inflation.
[0064] Sensors may be present within the lumen of perfusion catheter 220 , e.g. for detecting the temperature as well as perfusion pressure of the blood. The sensors are connected via a wired or wireless method to monitoring system 300 . In a preferred embodiment, separate wires are used to connect each sensor to monitoring system 300 .
[0065] Tip 221 of perfusing catheter 220 may be equipped with inflatable balloon 222 , as illustrated in FIG. 1, which may occlude coronary ostium completely. Alternatively, tip 221 of perfusing catheter 220 may be equipped with inflatable ring shape balloon, as illustrated in FIG. 2, or an inflatable butterfly shape balloon as illustrated in FIG. 3, that does not occlude the coronary ostium completely. FIG. 4 illustrates tip 221 of perfusing catheter 220 without inflatable balloon 222 .
[0066] In another embodiment, tip 221 of perfusing catheter 20 may have a specific space around tip 221 , e.g. annulus 221 a , operatively connected to a vacuum system (not shown in the figures). Upon engaging a portion of tip 221 into the coronary ostium, e.g. the first 2-3 mm, a negative pressure may be generated within this space to facilitate the attachment and fixation of perfusion catheter 220 in the coronary ostium. In such an embodiment, attaching perfusion catheter 220 to the aortic wall adjacent to the coronary ostium by vacuum eliminates the need for any inflatable balloon 222 .
[0067] Arterial introducer 202 may comprise ports 202 a , 202 b through which catheters, e.g. two perfusion catheters 220 , may be introduced and passed up to the coronary artery ostia. Ports 202 a , 202 b may also provide entry and exit points for channels and wires present with the catheters.
[0068] In a preferred embodiment, perfusion catheter 220 is substantially tubular with an outer wall defining an interior lumen. Distal end 221 of perfusion catheter 220 may comprise a pre-shaped curvature so that it may be engaged into the coronary artery ostia more readily. Perfusion catheter 220 may have balloon 222 at tip 221 .
[0069] As perfusion catheter may comprise a tubular portion, one or more lumen may extend throughout the length of perfusion catheter 220 to allow processed blood to be perfused to the coronary circulation. The lumen of perfusion catheter 220 may be adapted to connect to fluid outlet 104 (FIG. 1 a ) of multi-chambered dialysis machine 100 . As illustrated in FIG. 3 a , inflation channel 227 may be present within or proximate to the outer wall of perfusion catheter 220 for inflation of balloon 222 .
[0070] One or more sensors may be disposed proximate or within the lumen of perfusion catheter 220 such as for detecting blood temperature, perfusion pressure of the blood, or the like, or a combination thereof. Sensors may be connected to monitoring system 300 , e.g. using wired or wireless connections, for detection and/or monitoring of blood temperature and pressure respectively.
[0071] The lumen of perfusing catheters 220 should have sufficient internal diameter to allow a flow rate of about at least 150 ml/min for processed blood, with a preferred range being 150-250 ml/min. Further, perfusing catheters 220 should be able to maintain a safe coronary perfusion pressure of about 100-150 mmHg in case of complete isolation of coronary artery.
[0072] Perfusion catheter 220 may further contain inflation channel 238 (FIG. 4 a ) proximate the outer wall. Inflation channel 238 may be in fluid communication with and help inflate inflatable balloon 222 .
[0073] In one embodiment, inflatable balloon 222 may occlude the coronary ostium completely when inflatable balloon 222 is inflated (FIG. 4 b ). Alternatively, inflatable balloon 222 may be ring-shaped (FIG. 4 c ) or butterfly-shaped (FIG. 4 d ) so that inflatable balloon 222 cannot occlude the coronary ostium completely when it is inflated.
[0074] One or more lumen may extend throughout the length of perfusion catheter 220 through which the processed blood may be perfused to the coronary circulation. Lumen of perfusion catheter 220 may be fluidly connected to fluid outlet 104 (FIG. 1 a ) of multi-chambered dialysis machine 100 .
[0075] In an embodiment, two sensors are disposed proximate or within lumen of perfusion catheter 220 for detecting temperature as well as perfusion pressure of the blood. The sensors may be connected via two separate wires to monitoring system 300 for detection of blood temperature and pressure respectively.
[0076] Referring now to FIG. 3, an illustration of vehicle catheter 230 with aortic root ring 232 , vehicle catheter 230 may be introduced through femoral artery 30 (FIG. 5 a ) of patient 10 and may comprise pre-shaped curvature 239 proximate tip 231 where pre-shaped curvature 239 may be compatible with aortic arch 22 (FIG. 5 a ). Throughout the length of vehicle catheter 230 , one or more channels, e.g. 233 - 234 (FIG. 3 a ), may be present, e.g. channel 233 for monitoring the blood pressure within the ascending aorta, inflation channel 234 disposed proximate wall 235 , and the like.
[0077] Inflatable aortic root ring 232 may be present at tip 231 and may be in fluid communication with inflation channel 234 for inflating and/or deflating inflatable aortic root ring 232 . Inflatable aortic root ring 232 may be used to help stabilize vehicle catheter 230 in aortic arch 22 when inflatable aortic root ring 232 is inflated.
[0078] In an embodiment, two or more perfusion catheters 220 may be contained at least partially or otherwise housed within vehicle catheter 230 .
[0079] [0079]FIG. 5 illustrates vehicle catheter 230 without aortic root ring 232 . A single vehicle catheter 230 with a pre-formed curvature at tip 231 compatible with the aortic arch may be introduced through femoral artery 30 up to the ascending aorta above the coronary ostia. Channel 233 may extend throughout the length of vehicle catheter 230 where channel 233 is adapted for use in monitoring the blood pressure within the ascending aorta. Two or more perfusion catheters 220 may be at least partially contained or housed within lumen of vehicle catheter 230 .
[0080] Vehicle catheter 230 may be equipped with aortic root ring 232 . In an embodiment, after perfusion catheter 220 housed within vehicle catheter 230 is engaged into the coronary ostium, ring shape balloon 232 may be inflated, e.g. using inflation channel 234 , to stabilize vehicle catheter 230 within the aortic root (FIG. 6C).
[0081] In the operation of several exemplary embodiments, coronary dialysis system 1 and its methods of use comprise a capability to be used not only for patient 10 already suffering from chronic coronary artery disease but also its usage in the setting of acute coronary syndrome (“ACS”), e.g. unstable angina and acute myocardial infarction, to decrease plasma factors which affecting the short and long term survival of patients. Corornary dialysis system 1 and/or multi-chambered dialysis machine 100 may be used with patients 10 known to be suffering from coronary artery disease in a stable clinical situation as well as implemented in an ACS setting in order to reduce the plasma level of harmful and toxic factors such as CRP, tissue factor as well as fibrinogen released during acute coronary syndrome. Consequently, the complication, morbidity and mortality of acute coronary syndrome may be reduced.
[0082] Coronary dialysis system 1 may be used to deliver ante grade, local, direct, and high dose of therapeutic agents such as HDL, genes, chelating agents, and statin to coronary arterial system. A high level of therapeutic agents may be maintained in the intimate vicinity of coronary endothelial cells by preventing dilution of processed blood by the systemic circulation. Hence, maximal therapeutic effects may be obtained.
[0083] Accordingly, one or more methods of using coronary dialysis system 1 comprises use of multi-chambered coronary dialysis machine 100 to perform one or more specific functions, which can be accomplished in a specific, e.g. serial, order to reduce risk factors of atherosclerosis, prevent the progression of atherosclerosis, and/or prevent the occurrence of acute and chronic complications of atherosclerosis such as acute coronary syndrome and congestive heart failure. These methods may be used to deliver a number of therapeutic agents locally into the coronary system. Representative therapeutic agents may include, but are not limited to, statins, anti-inflammatory agent, angiotensin converting enzyme inhibitor, peroxisome proliferator-activated receptor agonist, HDL, apolipoprotein apoA1, mutated apolipoprotein apoA1, gene for gene therapy and chelating agent. Further, harmful and/or unwanted substances may be removed from the blood. Examples of these substances include cholesterol, LDL, triglyceride, perfused HDL, C-reactive protein, Lp (a), fibrinogen, tissue factor, interleukine, interleukine 1, interleukine 6, TNF-alpha, chemoattractant molecules, CD 14, C3 complement, C4 complement, and C 1 inhibitor.
[0084] Moreover, presence of an inappropriate high plasma level of drugs or any added agents may be prevented by plasmaphaeresis as well as aphaeresis in multi-chambered dialysis machine 100 . Consequently, the coronary circulation may be perfused with appropriate level of drugs and other substances that make the plaque stable (e.g. HDL may mobilize cholesterol from peripheral tissue through reverse cholesterol transport), and harmful and/or unwanted substances such as LDL may be removed from the processed blood through processing (e.g. aphaeresis) in multi-chambered dialysis machine 100 .
[0085] Coronary dialysis system 1 may be used to access the circulatory system from a peripheral venous site or a peripheral induced shunt in order to establish rapid and aggressive therapy for treatment of patient and his coronary vulnerable plaques. Coronary dialysis system 1 may further be used to provide continuous delivery of high doses of affecting drugs (such as cholesterol removal drugs, anti inflammatory, anti thrombotic, thrombolytic therapy, and/or chelating agents, or the like, or combinations thereof), and genes for treatment of cardiovascular diseases such as coronary atherosclerosis and acute coronary syndrome. Coronary dialysis system 1 allows delivery of dosages, including high dosages, of substances such as HDL in order to facilitate enforce, and potentates their effect on atherosclerotic plaque. For example, during high dose delivery of chelating agents and genes other therapeutic modalities may be followed.
[0086] Referring now to FIG. 5 a , in several preferred embodiments, coronary dialysis system 1 is configured as a substantially closed fluid circuit in which the cardiac circulatory system of patient 10 may be completely isolated from systemic circulation. In this embodiment, collecting catheter 210 , perfusing catheter 220 , multi-chambered dialysis machine 100 , and the circulatory system of patient 10 —e.g. the coronary arterial tree, cardiac capillary system, and cardiac venous system of patient 10 —are incorporated in series in a loop circuit.
[0087] Collecting catheter 210 may be introduced at a left subclavian vein, right subclavian vein, right jugular vein, and/or femoral vessels 30 , 32 (FIG. 8).
[0088] Referring now to FIG. 6 a , in one such embodiment, after introducing vehicle catheter 230 through arterial sheath 202 and inflating ring shaped balloon 232 to fix vehicle catheter 230 in the ascending aorta, one or more perfusing catheters 220 specifically designed for individual coronary ostium are introduced and engaged appropriately in each desired coronary artery, e.g. through femoral artery 30 . Ostia may be occluded by inflating balloons 222 (FIG. 2) at tips 221 (FIG. 2) of perfusing catheters 220 . If inflatable balloon 212 is present, it may either substantially occlude or partially occlude coronary sinus 27 . For example, at the end of the cardiac venous drainage system, e.g. at coronary sinus 27 (FIG. 5 c ), collecting catheter 210 with inflatable balloon 212 (not shown in the figures) at tip 211 (not shown in the figures) is engaged into coronary sinus 27 where inflatable balloon 212 is inflated. If inflatable balloon 212 is ring shaped, occlusion may occur. If inflatable balloon 212 is butterfly shaped, occlusion may not occur.
[0089] The venous blood of heart 20 is drained to multi-chambered dialysis machine 100 . Processed blood is returned to patient 10 via one or more perfusion catheters 220 into one or more blood vessels (FIG. 5 b ).
[0090] In general, these methods may provide treatment such as stabilizing vulnerable plaques, decreasing the lipid content of the plaques, reducing inflammatory activity throughout the coronary system, decreasing the number of macrophages in the plaques and increasing the number of smooth muscle cells in the plaques. A number of coronary diseases such as atherosclerosis, chronic coronary artery disease, acute coronary syndrome, unstable angina, and acute myocardial infarction may be treated by these methods.
[0091] Using coronary dialysis system 1 , blood may be processed using plasmaphaeresis (primary plasma separation) and aphaeresis (plasma secondary separation). In general, based on plasmaphaeresis and aphaeresis, multi-chambered dialysis machine 100 may reduce harmful substances from blood through the processes of precipitation, filtration, adsorption, immune precipitation, immunoabsorption, or the like, or a combination thereof, e.g. by using micro-beads or nanoparticles.
[0092] After blood is withdrawn from patient 10 , as in the cases of conventional hemodyalysis in patients 10 suffering from renal failure, the blood is drained to multi-chambered dialysis machine 100 via fluid inlet 102 (FIG. 1 a ) to start processing in blood separation chamber 110 (FIG. 1 a ). By plasmapheresis, blood cells may be separated from plasma and the plasma may undergo a further step, e.g. apheresis. Using these steps, harmful and unwanted plasma substances may be separated from the plasma, e.g. LDL, triglyceride, CRP, Lp (a), fibrinogen, tissue factor, and several plasma cytokines such as interleukine 1 and 6, TNF-alpha, adhesion molecules (ICAM-1, VCAM-1), chemoattractant molecules such as monocyte colony stimulating factor, CD14, as well as 0 complement, C4 complement, and/or C1 inhibitor, or the like, or combinations thereof.
[0093] In an embodiment, plasma differential precipitation is applied for the elimination of LDL-cholesterol. After being separated from a hollow fiber module plasma will be acidified and heparinized. The precipitated plasma components are separated from a second hollow fiber module. The heparin excess is removed from the adsorption column from the plasma. The naturalized plasma after dialysis and ultra filtration will be re-admixed with blood cells. By implementing this method not only LDL but also a lot of the plasma substances will be co-precipitated and separated from plasma such as CRP, fibrinogen, tissue factor, CD14, LP (a), inter leukin-1, TNF alpha, inter leukin-6, C3, C4, C1 inhibitor, ferittin, and/or plasminogen, or the like, or combinations thereof.
[0094] Immunoabsorption (immunoprecipitation) using different ligands such as amino acids, protein, and polyclonal antibody is the mechanism that may be used to selectively precipitating and separating the plasma harmful materials including the factors mentioned above or even more other harmful factors.
[0095] In a preferred embodiment, blood may be warmed to an appropriate temperature, e.g. around 41-42° C. Heating the blood may not only directly subside inflammatory process but also, through melting and de-crystallization of cholesterol, may help plaque stabilization. Furthermore, blood heating to the febrile range has systemic effect that may decrease the plasma level of some cytokines such as TNF-alpha, IL-1, and IL-6. This heating process may be done in heater chamber 140 and/or in heat exchanger 122 .
[0096] Blood may be passed to Enricher 130 (FIG. 1 a ) in which dosages, including high dosages, of drugs and/or other therapeutic agents may be added to the passing blood to be delivered to the systemic circulation as well as coronary circulation in order to prevent atherosclerotic plaque progression and provide plaque stabilization. HDL, and its main apoprotein apoA-1, is the mainstay agent that may be perfused systemically.
[0097] Other classes of agents that could be utilized and perfused systemically may comprise genes such as gene encoding the apoA-1 in the liver to increase its production. Gene transfer to stabilize the vulnerable atherosclerotic plaque may prevent plaque rupture and subsequent thrombosis. Possible strategies include over-expressing TIMPs (tissue inhibitor of matrix metalloproteinase) and blocking the actions of pro-inflammatory molecules such as those of the transcription factor NF-kB.
[0098] Other agents that may be perfused comprise chelating agents such as EDTA to extract the calcium content of the atherosclerotic plaques throughout of the circulatory system of the body including coronary arteries.
[0099] Using this system which provides the procedure for specially removing APO-containing ffpoproteins from the body. This technique is based upon the precipitation of the positively charged LDL and other beta lipoprotein when heparin is added at low PH. In addition of LDL a number of other plasma proteins such as LP (a), fibrinogen, plasminogen, antithrombin, TNF alpha, CD14, CD40/CD40L, circulating adhesion molecules, and C3 and c4 are all co-precipitated.
[0100] Dyslipidemias remain important target for the development of novel therapies. Gene therapy is a logical therapeutic approach to monogenic lipoprotein disorder, such as homozygous familial hypercholesterolemia, familial lipoprotein lipase deficiency, familial LCAT deficiency, and abetalipoproteinemia for which current therapies are inadequate.
[0101] Gene therapy could theoretically stabilize the vulnerable plaque by reducing the plaque content in lipids and macrophages. Alternatively, the introduction into the atherosclerotic plaque of genes encoding for thrombolytic proteins or growth factors able to restore physiologic antithrombotic function of endothelial cells may inhibit thrombus formation should the plaque rupture. Although many technical challenges still lie ahead, recent developments indicate they are possibly within reach in the nottoo distant future.
[0102] Gene therapy could also be used to increase the expression of certain protein, such as apo a-1 as strategy to raise HDL cholesterol level or apo E as a strategy for severe combined hyper lipidemia. With further progress in development of vectors, gene therapy for severe dyslipidemia likely to become a clinical reality.
[0103] Liver directed gene transfer of human apoA-1 resulted in significant regression of the preexisting atherosclerotic lesion in LDL receptor deficient mice as assessed by important methods. Apo a-1 and LCAT are two potential targets for gene therapy in patients with atherosclerosis associated with a low HDL cholesterol level.
[0104] FGF-4(GENEREX) is a angiogenic gene therapy which triggers the production of a protein that stimulate new blood vessel growth providing an attractive route for blood to by pass clogged and blocked arteries in the heart. GENEREX in an one time non surgical delivery of an adenovirus vector containing the human FGF-4 in to the coronary arteries via a standard catheter.
[0105] PhVEGF-A165 injection directly in to myocardium at four sites in the anterolateral region of left ventricle was done. Plasma VEGF-165 increased peaking at sixth day. It has significant effect in decreasing angina pectoris, nitroglycerine intake and improving CCS. These improvements remained after 12 months. So intramyocardial injection of phVEGF-165 is safe and may lead to improved myocardial perfusion and function with longstanding symptomatic relief at end stage angina pectoris.
[0106] Chelation is the binding (and subsequent elimination) of harmful substances that are present in the bloodstream and in the walls of hardened and partially clogged blood vessels.
[0107] “EDTA” is a meta 1-complexing synthetic amino acid that acts as the “chelator.” “EDTA” chelation is a therapy by which repeated administrations of a weak synthetic amino acid (“EDTA,” ethylenediamine tetra-acetic acid) gradually reduce atherosclerotic plaque and other mineral deposits throughout the cardiovascular system by literally dissolving them away. “EDTA” infusion removes the calcium which is necessary for the formation of fibrinogen and coagulation from the blood stream.
[0108] The following exemplary method embodiments are given for the purpose of illustrating various embodiments of the invention and are not meant to limit the present invention in any fashion.
[0109] Referring still to FIG. 5 a , in a first method embodiment, arterial sheath 202 is introduced, such as by using Seldinger's method, after obtaining access site in femoral artery 30 . Two perfusion catheters 220 , one for each of two coronary arteries (FIG. 5 b ), may be introduced through vehicle catheter 230 . Distal end 221 of perfusion catheter 220 may have a pre-shaped curvature so that distal end 221 of perfusion catheter 220 may be engaged into the coronary artery ostia more readily. In a first exemplary method embodiment, there is no occluding balloon 222 so that the heart is not isolated from systemic circulation.
[0110] Collecting catheter 210 may be introduced, such as through the right subclavian vein or right jugular vein directly into right atrium 24 , to collect the venous blood and drain it to multi-chambered dialysis machine 100 for processing.
[0111] Alternatively, inflatable balloons, 212 and/or 222 may be present but may comprise a ring or butterfly shape on inflation that do not completely block the coronary ostia.
[0112] In this exemplary method embodiment, the re-circulating blood does not need to be oxygenated and coronary perfusion pressure is regulated by systemic blood flow. Processed blood, however, may be diluted by the systemic blood.
[0113] Referring now to FIG. 6 a , in a second method embodiment, arterial sheath 202 is introduced, such as by using Seldinger's method, after obtaining access site in femoral artery 30 . Two perfusion 220 , one for each of the two coronary arteries, may be introduced through arterial sheath 202 .
[0114] Collecting catheter 210 may be introduced, such as through the right subclavian vein or right jugular vein directly into right atrium 24 , to collect the venous blood and drain it to multi-chambered dialysis machine 100 for processing.
[0115] These catheters 210 and 220 have inflatable balloons at their tips, i.e. inflatable balloon 212 at tip 211 and inflatable balloon 222 at tip 221 . Inflatable balloons 212 , 222 may completely block the coronary ostia to isolate the coronary system from systemic circulation. In this exemplary method, processed blood is perfused directly to the coronary artery without dilution while maintaining a dose of drugs in direct contact to endothelial cells, including high doses of drugs. In this method, multi-chambered dialysis machine 100 further comprises oxygenator 120 (FIG. 1 a ) as well as pump 150 (FIG. 1 a ).
[0116] Referring now to FIG. 7, in a exemplary third embodiment, arterial sheath 202 is introduced, such as by using Seldinger's method, after obtaining access site in the femoral artery. Then a single catheter, vehicle catheter 230 with a pre-formed curvature at distal 231 which is compatible with aortic arch 22 , is introduced through arterial sheath 202 up to the ascending aorta above coronary ostia. Vehicle catheter 230 may or may not have an inflatable ring-shape balloon 232 at tip 231 for fixation and stabilization of vehicle catheter 230 in the ascending aorta.
[0117] Collecting catheter 210 is introduced and takes the venous blood out of patient 10 to multi-chambered dialysis machine 100 for processing. Collecting catheter 210 may be applied by introducing a pre-shaped collecting catheter 210 , such as through the left subclavian vein using Seldinger's method, to engage into coronary sinus 27 . After engaging collecting catheter 210 in the coronary sinus ostium, inflatable balloon 212 is inflated and coronary sinus 27 will be occluded. Collecting catheter 210 may then collect the venous blood of the heart and drain to multi-chambered dialysis machine 100 .
[0118] Currently contemplated variants of this embodiment are related coronary perfusing catheters 220 which may or may not have inflatable balloons 222 at their tips 221 . As discussed herein above, perfusing catheter 220 may comprise inflatable balloon 222 which completely or substantially completely occludes coronary artery ostia so that complete isolation of heart 20 may be achieved. Preferably the lengths of perfusing catheters 220 allow perfusing catheters 220 to be introduced via femoral artery 30 to the coronary ostia. The lengths of vehicle catheter 230 similarly should allow perfusing catheters 220 to be introduced via femoral artery 30 to aortic root 22 .
[0119] Distal end 221 of each perfusing catheter 220 may be preshaped with an appropriate curvature and angulations similar to those in standard coronary angiography catheter so that perfusing catheter 220 may be selectively introduced into each coronary ostium as coronary catheters. Alternatively, perfusing catheter 220 may be so designed that the curvature and angulations of tip 221 may be changed by implementing fibers along the length of perfusing catheter 220 to facilitate coronary engagement.
[0120] A fourth exemplary embodiment is similar to the third exemplary embodiment except perfusing catheter 220 either does not comprise balloon 222 or may comprise a non-occluding balloon 222 . Where perfusing catheter 220 does not comprise balloon 222 or comprises a non-occluding balloon 222 , dilution of processed blood by systemic blood and instability of catheters 220 at coronary ostia may be of concern. However, co-perfusion of the coronary artery by systemic circulation omits the necessity of providing oxygenator 120 (FIG. 1 a ).
[0121] Referring now to FIG. 8, a fifth exemplary embodiment is similar to the exemplary embodiments above except that perfusion catheter and collection catheters are introduced through femoral vessels, e.g. 30 and 32 , rather than using a subclavian vein.
[0122] Referring now to FIG. 9, in a sixth exemplary embodiment systemic dialysis may be obtained by fitting patient 10 with collection catheter 210 and perfusion catheter 220 , e.g. using femoral artery 30 and femoral vein 32 . In this embodiment, oxygenator 120 may not be required. Further, use of inflatable balloons 222 , 232 may not be required.
[0123] Referring now to FIG. 10, in a seventh exemplary embodiment, fluids within the pericardium, as well as external heart tissue, may be remediated by introducing collection catheter 210 and perfusion catheter 220 into the space intermediate the pericardium and the heart. As with the methods described herein above, fluid may be withdrawn, processed, and returned to the space intermediate the pericardium and the heart. In an embodiment, entry into the pericardium may be accomplished via the aorta.
[0124] It will be understood that various changes in the details, materials, and arrangements of the parts which have been described and illustrated above in order to explain the nature of this invention may be made by those skilled in the art without departing from the principle and scope of the invention as recited in the appended claims. | The present invention relates generally to a system and methods for local delivery of drugs directly to the coronary circulation which may be isolated from systemic circulation. More especially it relates to a dialysis system and methods of infusing beneficial drugs, therapeutic agents, and/or other beneficial substances, including high doses of these, such as HDL, therapeutic genes, and/or chelating agents to the coronary system. The multi-chambered dialysis machine in the present system is capable of removing unwanted/harmful substances from the blood, enriching and/or otherwise processing the blood, and re-circulating the processed blood back to the coronary circulation of patient. It is emphasized that this abstract is provided to comply with the rules requiring an abstract which will allow a searcher or other reader to quickly ascertain the subject matter of the technical disclosure. It is submitted with the understanding that it will not be used to interpret or limit the scope or meaning of the claims. | 0 |
This is a division of application Ser. No. 07/828,433 filed Jan. 30, 1992, now U.S. Pat. No. 5,143,944.
TECHNICAL FIELD
The present invention relates to tertiary amine catalysts for catalyzing the urethane reaction in making polyurethane foam.
BACKGROUND OF THE INVENTION
Polyurethane foams are widely known and used in automotive, housing and other industries. Foam is generally referred to as rigid, microcellular, or flexible. Typically, in the preparation of polyurethane foams, a tertiary amine catalyst is used to accelerate the reaction of the polyisocyanate with water to generate carbon dioxide as a blowing agent and to accelerate the reaction with polyols to promote gelling. Tertiary amines generally are malodorous and offensive, and many have high volatility due to low molecular weight. Release of tertiary amine during foam processing may present significant safety and toxicity problems, and release of residual amines from consumer products is generally undesirable.
Amine catalysts which contain primary and/or secondary hydroxyl functionality typically have limited volatility and low odor when compared to related structures which lack this functionality. Furthermore, catalysts which contain hydroxyl functionality chemically bond into the urethane during the reaction and are not released from the finished product. Catalyst structures which embody this concept are typically of low to moderate activity and are designed to promote primarily the blowing (water-isocyanate) reaction.
U.S. Pat. No. 4,957,944 discloses certain dimethylamino alkyleneoxy isopropanols for use as a catalyst for preparing polyurethane foam.
U.S. Pat. No. 5,071,809 discloses tertiary amine catalysts containing secondary alcohol functionality for use in preparing polyurethane foams. The tertiary amines containing secondary alcohol functionality are prepared by reacting an olefinic nitrile with an aliphatic polyol having at least one secondary hydroxyl functionality, followed by reductive alkylation of the resulting cyanoalkylated polyol with a secondary aliphatic or cycloaliphatic amine, including those containing hetero atoms.
U.S. Pat. No. 4,590,223 discloses the preparation of tertiary amines containing secondary alcohols by reacting N-alkylpiperazines with an alkyleneoxide.
Secondary alcohol functionality is preferred in these structures because the catalysts exhibit a desirable balance between their promotion of the water-isocyanate reaction and their own reactivity with isocyanates. In contrast, catalysts which contain primary alcohols react rapidly with isocyanates and thus high use levels are required. Catalysts which contain tertiary alcohols react slowly with isocyanates, but the urethanes which are formed from the tertiary alcohols have poor thermal stability. See G. Oertel, ed. "Polyurethane Handbook," Hanser Publishers, Munich, 1985, pp. 82, 84 and H. J. Fabris, "Advances in Urethane Science and Technology," Vol. 6, Technomic Publishing Co., Westport, CT, 1978, pp. 173-179. These urethanes may degrade and release the catalysts at temperatures substantially below the decomposition temperature of the foam itself. The free amine could then accelerate foam decomposition.
A catalyst which strongly promotes the polyol-isocyanate (gelling) reaction is necessary for the manufacture of many polyurethane foams. Triethylenediamine (1,4-diazabicyclo[2.2.2.]octane) is widely used for this purpose. Quinuclidine (1-azabicyclo[2.2.2.]octane) can also be used as a gelling catalyst, particularly when the polyol contains a preponderance of secondary hydroxyl groups (U.S. Pat. No. 3,036,021). Quinuclidine is more reactive than triethylenediamine for the production of polyurethane foams. Both triethylenediamine and quinuclidine are volatile materials which will not remain trapped in the foam.
U.S. Pat. No. 3,036,021 also discloses that 1-azabicyclooctanes and their alkyl, amino, hydroxyl, nitro, alkoxy and halogen derivatives can also be used as gelling catalysts, although no distinctions were made with regard to the effect of catalyst structure on activity or suitability for incorporation into a foam.
U.S. Pat. No. 4,186,040 discloses a solid, pyrotechnic composition for dissemination of 3-quinuclidinyl benzylete, the composition consisting essentially of 3-quinuclidinyl benzylete and an oxidizer incorporated in a solid foamed polyurethane binder. No information is provided on the utility of quinuclidinyl benzylete as a catalyst or as a TEDA replacement. Furthermore, quinuclidinyl benzylete does not remain trapped in the foam.
SUMMARY OF THE INVENTION
The present invention provides a catalyst composition for catalyzing the trimerization of an isocyanate and/or the reaction between an isocyanate and a compound containing a reactive hydrogen, e.g., the urethane reaction for making polyurethane. The catalyst composition is a family of hydroxyfunctional amines which comprises 3-quinuclidinol, alternatively 3-hydroxy-1-azabicyclo[2.2.2.]octane, as represented by the following formula I and the alkoxylated derivatives of 3-quinuclidinol as represented by the following formula II: ##STR2## where R is hydrogen, a C 1 -C 8 alkyl, C 6 -C 10 aryl, or C 7 -C 10 aralkyl group; and
n is 1-3.
Compositions comprising mixtures of 3-quinuclidinol and compounds of formula II in which "n" is within the specific range are particularly preferred as catalysts, e.g., in such mixtures "n" would be 0-3, and most desirably "n" is 0 and 1.
As an advantage of the catalyst compositions, they strongly promote the polyol-isocyanate (gelling) reaction and are subsequently incorporated into the polyurethane product.
Another embodiment of the present invention is a polyurethane foam prepared by reacting a polyisocyanate, a polyol, water, cell stabilizer and a catalyst composition which comprises the hydroxyl functional amines of at least one of the above formulas I and II.
DETAILED DESCRIPTION OF THE INVENTION
The catalyst compositions according to the invention can catalyze the reaction between an isocyanate functionality and an active hydrogen-containing compound, i.e. an alcohol, an amine or water, especially the urethane (gelling) reaction to make polyurethanes and the blowing reaction of water with isocyanate to release carbon dioxide for making foamed polyurethanes, or the trimerization of the isocyanate functionality to form polyisocyanurates.
The polyurethane products are prepared using suitable organic polyisocyanates well known in the art including, for example, hexamethylene diisocyanate, phenylene diisocyanate, toluene diisocyanate ("TDI") and 4,4'-diphenylmethane diisocyanate ("MDI"). Especially suitable are the 2,4- and 2,6-TDIs individually or together as their commercially available mixtures. Other suitable isocyanates are mixtures of diisocyanates known commercially as "crude MDI", also known as PAPI, which contain about 60% of 4,4'-diphenylmethane diisocyanate along with other isomeric and analogous higher polyisocyanates. Also suitable are "prepolymers" of these polyisocyanates comprising a partially prereacted mixture of polyisocyanates and polyether or polyester polyols.
Illustrative of suitable polyols as a component of the polyurethane composition are the polyalkylene ether and polyester polyols. The polyalkylene ether polyols include the poly(alkylene oxide) polymers such as poly(ethylene oxide) and poly(propylene oxide) polymers and copolymers with terminal hydroxyl groups derived from polyhydric compounds, including diols and triols; for example, among others, ethylene glycol, propylene glycol, 1,3-butane diol, 1,4-butane diol, 1,6-hexane diol, neopentyl glycol, diethylene glycol, dipropylene glycol, pentaerythritol, glycerol, diglycerol, trimethylol propane and like low molecular weight polyols.
In the practice of this invention, a single high molecular weight polyether polyol may be used. Also, mixtures of high molecular weight polyether polyols such as mixtures of di- and tri-functional materials and/or different molecular weight or different chemical composition materials may be used.
Useful polyester polyols include those produced by reacting a dicarboxylic acid with an excess of a diol, for example, adipic acid with ethylene glycol or butanediol, or reacting a lactone with an excess of a diol such as reacting caprolactone with propylene glycol.
In addition to the polyether and polyester polyols, the masterbatches, or premix compositions, frequently contain a polymer polyol. Polymer polyols are used in polyurethane foam to increase the foam's resistance to deformation, i.e. to increase the load-bearing properties of the foam. Currently, two different types of polymer polyols are used to achieve load-bearing improvement. The first type, described as a graft polyol, consists of a triol on which vinyl monomers are graft copolymerized. Styrene and acrylonitrile are the usual monomers of choice. The second type, polyurea modified polyols, is a polyol containing a polyurea dispersion formed by the reaction of a diamine and TDI. Since TDI is used in excess, some of the TDI may react with both the polyol and polyurea. This second type of polymer polyol has a variant called PIPA polyol which is formed by the in-situ polymerization of TDI and alkanolamine in the polyol. Depending on the load-bearing requirements, polymer polyols may comprise 20-80% of the polyol portion of the masterbatch.
Other typical agents found in the polyurethane foam formulations include crosslinkers such as ethylene glycol, butanediol, diethanolamine, diisopropanolamine, triethanolamine and/or tripropanolamine; blowing agents such as water, methylene chloride, trichlorofluoromethane and the like; and cell stabilizers such as silicones.
A general polyurethane flexible foam formulation containing the catalyst composition according to the invention would comprise the following components in parts by weight (pbw):
______________________________________Flexible Foam Formulation Parts by Weight______________________________________Polyol 20-80Polymer Polyol 80-20Silicone Surfactant 1-2.5Blowing Agent 2-4.5Crosslinker 0.5-2Catalyst 0.5-2Isocyanate Index 92-115______________________________________
The urethane catalyst composition consists essentially of 3-quinuclidinol or a 3-quinuclidinol derivative compound of the following general formula II, or a mixture thereof: ##STR3## where R is a hydrogen, C 1 -C 8 alkyl, C 6 -C 10 aryl or C 7 -C 10 aralkyl group; and
n is 1-3, preferably 1-2, and most preferably n is 1. For mixtures of compounds suitable as catalyst compositions (based on formula II), n is 0-3, preferably 0-2, and most preferably 0-1. For 3-quinuclidinol, n is 0 in formula II. Preferred mixtures which are liquid products would comprise 0 to 85 wt %, preferably 50 to 85 wt %, 3-quinuclidinol and 15 to 100 wt %, preferably 15 to 50 wt %, derivatives of formula II, provided that the derivative in which n is 3 and higher oligomers comprise no greater than 50 wt % of the mixture.
These mixtures can be prepared by simply blending the desired amounts of 3-quinuclidinol and appropriate derivatives or, in some cases by reacting 3-quinuclidinol with an appropriate amount of alkylene oxide.
Alkyl groups would include, for example, methyl, ethyl, butyl, ethylhexyl and the like; aryl groups would include, for example, phenyl, p-tolyl and the like, and aralkyl groups would include, for example, benzyl, phenethyl and the like. It is preferred that R be methyl.
The 3-quinuclidinol may be prepared by the procedure of U.S. Pat. No. 3,464,997. It is also commercially available, being marketed by Janssen Chemical and Aldrich Chemicals.
The alkoxylated derivatives of 3-quinuclidinol can be prepared by reacting 3-quinuclidinol with an alkylene oxide of the formula ##STR4## where R is hydrogen, C 1 -C 8 alkyl, C 6 -C 10 aryl or C 7 -C 10 aralkyl, in the presence of a base catalyst in a dipolar aprotic solvent at temperatures ranging from RT up to the boiling point of the solvent and at pressures up to autogenous pressure. It is preferred that R be H or methyl, especially methyl. The alkylene oxide and the 3-quinuclidinol can be reacted in a 0.2:1 to 10:1 mole ratio range, preferably 1:1 to 3:1.
These derivatives of 3-quinuclidinol for the most part can be represented by formula II; however, lesser amounts of compounds involving ##STR5## linkages could also be present in the reaction products.
A catalytically effective amount of the catalyst composition is used in the polyurethane formulation. More specifically, suitable amounts of the catalyst composition may range from about 0.01 to 10 parts per 100 parts by weight polyol in the polyurethane formulation.
The catalyst compositions may be used in combination with other tertiary amine and organotin urethane catalysts well known in the urethane art.
EXAMPLE 1
In this example a polyurethane foam was prepared in a conventional manner. The polyurethane formulation in parts by weight was:
______________________________________COMPONENT PARTS______________________________________Multranol 9151 70Multranol 9143 30Water 4.2Diethanolamine 1.74DC 5164 1.0TDI 80 105 index______________________________________
Multranol 9151 polyol--polyurea filled, ethylene oxide tipped polyether polyol marketed by Mobay Corp.
Multranol 9143 polyol--ethylene oxide tipped, conventional polyether polyol marketed by Mobay Corp.
DABCO DC 5164 silicone surfactant marketed by Air Products and Chemicals, Inc.
TDI 80--a mixture of 80 wt % 2,4-TDI and 20 wt % 2,6-TDI.
The foam reactivity was measured using 33 wt % 3-quinuclidinal (3-QND) in ethylene glycol or DABCO 33LV® catalyst (33 wt % triethylenediamine in dipropylene glycol) as gelling catalysts and DABCO® BL-11 catalyst [70 wt % bis(dimethylaminoethyl)ether in dipropylene glycol] as the blowing catalyst. The activity of 3-QND was also compared to that of DABCO 33LV® catalyst in the absence of a cocatalyst. Table 1 sets forth conditions and results.
TABLE 1______________________________________ 3-QND/ DABCO 33LV/ DABCO DABCOCatalyst DABCO BL-11 BL-11 33LV 3-QND______________________________________Amount (parts) 0.42/0.15 0.42/0.15 1.26 1.26Top of Cup 1 11.3 10.5 11.6 10.6(sec)Top of Cup 2 47.6 40.5 40.0 43.3(sec)String Gel (sec) 65.6 61.8 63.6 69.0Full Rise Time 132.1 141.3 112.1 142.0(sec)______________________________________
Times cited were from mixing of the polyol masterbatch with isocyanate. Top Cup 1 represents the time required for the foam formulation to fill a 16 oz cup and is an indication of reaction initiation. Top Cup 2 represents the time required for the foam formulation to fill a 1 gal cup in addition to the 16 oz cup mentioned above and is an indication of reaction progression. String Gel and Full Rise are further measures of reaction progression and provide some indication of extent of cure.
The advantage of 3-quinuclidinol is that it provides an excellent reactivity match for triethylenediamine during the critical early stages of the foaming reaction, and is then incorporated into the polymer, as seen in the increased full rise time measurement. Furthermore, the amount of 3-quinuclidinol can be increased to shorten the full rise time, but volatile emissions for the final product will not increase.
EXAMPLE 2
The example shows the propoxylation of 3-quinuclidinol.
To 25 g (197.1 mmol) of 3-quinuclidinol suspended in 30 mL of N,N-dimethylformamide (DMF) was added 0.0356 g (0.89 mmol) of sodium hydroxide catalyst. The mixture was heated to 65° C. with stirring. Propylene oxide (103.22 g, 592 mmols) was added dropwise while maintaining the temperature between 70° to 76° C. The 3-quinuclidinol conversion was 98.5%. The DMF was removed by vacuum distillation, and the residue fractionated by Kugelrohr distillation. Selected fractions were designated Propoxylate 1-3 and were tested as described in Example 3 and Table 2.
EXAMPLE 3
This example demonstrates the relative reactivity of the 3-quinuclidinol derivatives.
The rate of isocyanate consumption as a function of time was measured using a formulation similar to that of Example 1, but containing monofunctional reactants. Reaction samples drawn at the indicated times were quenched with dibutylamine and analyzed by liquid chromatography. The catalysts were compared on an equimolar basis corresponding to a loading of 0.35 parts per hundred parts of DABCO 33LV catalyst in the formulation in Example 1. Table 2 sets forth the results.
TABLE 2______________________________________% NCO Conversion Time (min)Catalyst 0.5 1.0 1.5 2.0 3.0 4.0 5.0 6.0______________________________________Triethylene- 14.2 28.9 44.0 50.3 64.1 71.6 76.5 79.9diamine3-Quinu- 18.9 34.2 46.4 54.3 66.2 72.7 76.6 79.2clidinolPropoxy- 16.2 29.6 41.6 50.4 64.3 71.4 76.2 79.3late 1.sup.aPropoxy- 16.1 28.7 40.3 48.6 59.4 65.6 69.5 72.3late 2.sup.bPropoxy- 7.2 14.3 19.8 28.7 42.2 50.8 58.4 63.9late 3.sup.cHydro- 7.9 17.8 25.5 32.1 41.9 49.7 54.6 59.9quinine.sup.d______________________________________ .sup.a Propoxylate 1 contains 2.7% 3quinuclidinol, 70.0% monopropoxylate (Formula II, n = 1) and 27.3% dipropoxylate (Formula II, n = 2) on a mole basis. .sup.b Propoxylate 2 contains 17.1% monopropoxylate, 59.6% dipropoxylate, and 16.4% tripopoxylate on a mole basis. .sup.c Propoxylate 3 contains 6.6% dipropoxylate, 79.9% tripropoxylate, and 9.2% tetrapropoxylate on a mole basis. ##STR6##
The uniqueness of the propoxylated 3-quinuclidinol derivatives is that the retain the desirable high activity of 3-quinuclidinol itself, as well as the necessary secondary alcohol functionality, but are liquids readily soluble in a variety of common catalyst carriers; e.g., dipropylene glycol. 3-Quinuclidinol, itself, is a high melting solid with limited solubility and thus is not convenient for all applications. Hydroquinine, although it also contains a secondary alcohol, is poorly active. Desirable activity is obtained if substitutes are placed on the 3-position, rather than the 2-position, of 1-azabicyclo[2.2.2.]octane. The size of the substituent on the 3-position may also influence the level of activity, as shown by the comparison of the results for propoxylate 3 to those for hydroquinine.
EXAMPLE 4
This example demonstrates the partial propoxylation of 3-quinuclidinol.
3-Quinuclidinol (39.4 mmols, 5.01 g), sodium hydroxide (0.2 mmol, 0.008 g), and DMF (10 mL) were charged to a 50 mL 3-neck roundbottom flask equipped with a magnetic stir bar, thermometer, reflux condenser and a septum. Propylene oxide (19.7 mmols, 1.14 g) was added by syringe over 5 minutes while stirring and heating the solution to 60° C. The temperature rose 5°-10° C. following the propylene oxide addition, and gradually dropped back to 60° C. over the next 15 minutes. The DMF was removed by heating the reaction to 40° C. at 500 mTorr for several hours. The product was a liquid.
The experiment was repeated as above with 39.7 mmols (5.05 g) of 3-quinuclidinol and 40.0 mmols (2.31 g) of propylene oxide, the other reagents and conditions remaining unchanged. The samples were analyzed by gas chromatography to determine the extent of propoxylation. The results are tabulated below.
______________________________________3-Qui- Pro- % Area by GCnucli- pylene 3-Qui-dinol Oxide nucli- mono- di- tri-Run (mmols) (mmols) DMF dinol PO PO PO______________________________________4A 39.4 19.7 2 85 8 2 14B 39.7 40.0 0.6 54 22 9 11______________________________________
EXAMPLE 5
In this example a polyurethane foam was prepared in a conventional manner. The polyurethane formulation in weight parts was:
______________________________________Component Parts______________________________________Pluracol-816 40Pluracol-973 60Water 3.5Diethanolamine 1.49DC 5043 1.5TDI 80 105 index______________________________________
Pluracol-816 polyol--ethylene Oxide tipped, conventional polyether polyol marketed by BASF AG.
Pluracol-973 polyol--styrene-acrylonitrile filled, ethylene oxide tipped polyether polyol marketed by BASF AG.
DABCO DC 5043 silicone surfactant marketed by Air products and Chemicals, Inc.
The foam reactivity was measured using DABCO 33LV catalyst, Run 4A catalyst (50 wt % in water) or Run 4B catalyst (50 wt % in water) as gelling catalysts and DABCO BL-11 catalyst as the blowing catalyst. Table 3 sets forth conditions and results.
TABLE 3______________________________________ Run 4A/ Run 4B/ DABCO 33LV/ DABCO DABCOCatalyst DABCO BL-11 BL-11 BL-11______________________________________Level (parts) 0.50/0.15 0.41/0.15 0.54/0.15Top of Cup 1 (sec) 10.2 10.7 11.3Top of Cup 2 (sec) 32.3 35.2 34.9String Gel (sec) 68.8 64.0 64.1Full rise time (sec) 99.3 94.3 98.1______________________________________
The results in Table 3 indicate that mixtures containing 3-quinuclidinol and propoxylated 3-quinuclidinol have activity comparable to that of triethylenediamine at equimolar use levels. Furthermore, the partially propoxylated mixtures are liquids which are more convenient to handle than 3-quinuclidinol itself.
The prior art high activity amine gelling catalysts are fugitive in that they can escape from a foam during or after its manufacture. The present invention successfully incorporates secondary alcohol functionality into high activity gelling catalysts which display activity similar to that of TEDA, the industry standard. The secondary alcohol functionality lowers the volatility of the catalysts of the invention and prevents their escape from the finished foam product through the chemical reaction with the foam itself. Moreover, the catalyst compositions are liquids which are easily processed and show negligible activity loss as compared to 3-quinuclidinol.
The prior art does not indicate that quinuclidine or its derivatives would be expected to have activity very similar to that of TEDA. An activity match is desirable so that the catalysts for the present invention can be easily employed as drop-in replacements for TEDA.
STATEMENT OF INDUSTRIAL APPLICATION
The present invention provides compositions for catalyzing the urethane reaction and preparing urethane products, especially polyurethane foam products. | A method for preparing a polyurethane foam which comprises reacting an organic polyisocyanate and a polyol in the presence of a blowing agent, a cell stabilizer and a catalyst composition consisting essentially of at least one compound of the following formula: ##STR1## where R is hydrogen, C 1 -C 8 alkyl, C 6 -C 10 aryl or C 7 -C 10 aralkyl, and n is 0-3. The preferred catalyst consists essentially of the compound when n is 0, namely 3-quinuclidinol. | 2 |
FIELD OF THE INVENTION
[0001] The present invention relates to reaction products that are useful as antioxidants in organic materials normally susceptible to oxidative degradation in the presence of air or oxygen, such as petroleum products, synthetic polymers, and elastomeric substances and processes suitable for preparing such reaction products.
BACKGROUND OF THE INVENTION
[0002] It is well known that a wide variety of organic materials are susceptible to oxidative degradation in the presence of air or oxygen, especially when at elevated temperatures. Such organic materials include, for example, gasolines, diesel fuels, burner fuels, gas turbine and jet fuels, automatic transmission fluids, gear oils, engine lubricating oils, thermoplastic polymers, natural and synthetic rubber, and the like. Over the years, considerable efforts have been devoted to discovery and development of compounds capable of minimizing the degradation of one or more of such materials. As conditions of use and exposure of such materials to various oxygen containing environments change over the years, the desire for new effective oxidation inhibitors (a.k.a. antioxidants) continues. Also, the art benefits greatly if new and highly effective process technology is provided for producing known effective oxidation inhibitors.
[0003] U.S. Pat. No. 3,673,091 discloses forming oxidation inhibitors by the reaction between 3,5-di-tert-butyl-4-hydroxybenzyl alcohol and aryl amines, carbazole, phenazines, or acridines. Unfortunately, the resultant reaction product is a complex mixture containing large quantities of unreacted amine starting material and in which the desired products are formed in low yields.
SUMMARY OF THE INVENTION
[0004] In some embodiments, the present invention relates to macromolecular antioxidant products having properties enhancing their usefulness as oxidation inhibitors, especially for petroleum products of the types referred to above. These macromolecular reaction products comprise one or more i) heterocyclic compounds substituted with one 3,5-di-hydrocarbyl-4-hydroxylbenzyl group; ii) heterocyclic compounds substituted with two 3,5-di-hydrocarbyl-4-hydroxylbenzyl groups; iii) heterocyclic compounds substituted with three 3,5-di-hydrocarbyl-4-hydroxylbenzyl groups; iv) heterocyclic compounds substituted with four 3,5-di-hydrocarbyl-4-hydroxylbenzyl groups; v) one or more heterocyclic compounds substituted with five 3,5-di-hydrocarbyl-4-hydroxylbenzyl groups; and, vi) one or more methylene-bridged heterocyclic compounds substituted with one or more, in some embodiments in the range of from about 1 to about 12, 3,5-di-hydrocarbyl-4-hydroxylbenzyl groups.
[0005] Preferred macromolecular antioxidant products of the present invention are compounds that are liquid at room temperatures (about 23° C.) or solids that melt at less than about 100° C., preferably about 60° C., and that are capable of being dissolved in common organic solvents and especially in liquid hydrocarbon solvents. In addition, in many cases these products have higher solubility in lubricants such as, for example, a base oil consisting of 50% by volume of high viscosity index 100 Neutral and 50% by volume of high viscosity index 250 Neutral such as referred to in U.S. Pat. No. 3,673,091.
[0006] Still another aspect of this invention is the provision of new antioxidant formulations especially adapted for use in lubricating oils, and especially in lubricating oils for internal combustion engines. These and other antioxidant formulations are also described in detail hereinafter.
[0007] The above and other aspects, features, and embodiments of this invention will be still further apparent from the ensuing description and appended claims.
DETAILED DESCRIPTION OF THE INVENTION
Reaction Products of the Present Invention
[0008] As noted above, the macromolecular reaction products of the present invention are useful as antioxidants; thus, these macromolecular reaction products are sometimes referred to herein as alkylated heterocyclic compounds, antioxidant products, macromolecular antioxidant compositions, or macromolecular oxidation inhibitors for simplicity. As stated above, preferred antioxidant products of the present invention are compounds that are liquid at room temperatures (about 23° C.) or solids that melt at less than about 100° C., preferably about 60° C., and that are capable of being dissolved in common organic solvents and especially in liquid hydrocarbon solvents. In addition, in many cases these products have higher solubility in lubricants such as, for example, a base oil consisting of 50% by volume of high viscosity index 100 Neutral and 50% by volume of high viscosity index 250 Neutral such as referred to in U.S. Pat. No. 3,673,091.
[0009] The antioxidant products of the present invention typically comprise one or more heterocyclic compounds substituted with one or more 3,5-di-hydrocarbyl-4-hydroxylbenzyl group(s), and one or more heterocyclic compounds substituted with one or more 3,5-di-hydrocarbyl-4-hydroxylbenzyl group(s) and having a methylene bridge. The alkylated heterocyclic compound typically comprise one or more i) heterocyclic compounds substituted with one 3,5-di-hydrocarbyl-4-hydroxylbenzyl group; ii) heterocyclic compounds substituted with two 3,5-di-hydrocarbyl-4-hydroxylbenzyl groups; iii) heterocyclic compounds substituted with three 3,5-di-hydrocarbyl-4-hydroxylbenzyl groups; iv) heterocyclic compounds substituted with four 3,5-di-hydrocarbyl-4-hydroxylbenzyl groups; v) heterocyclic compounds substituted with five 3,5-di-hydrocarbyl-4-hydroxylbenzyl groups; and vi) one or more methylene-bridged heterocyclic compounds substituted with one or more, in some embodiments in the range of from about 1 to about 12, 3,5-di-hydrocarbyl-4-hydroxylbenzyl groups. It is preferred that the macromolecular reaction products of the present invention contain less than about 10 wt. % of heterocyclic compounds substituted with one 3,5-di-hydrocarbyl-4-hydroxylbenzyl groups, based on the total weight of the reaction product. In other embodiments the reaction products of the present invention contain 25 wt. % or less of heterocyclic compounds substituted with two 3,5-di-hydrocarbyl-4-hydroxylbenzyl groups, on the same basis. In still other embodiments the antioxidant products of the present invention contain 25 wt. % or less of heterocyclic compounds substituted with one 3,5-di-hydrocarbyl-4-hydroxylbenzyl group and heterocyclic compounds substituted with two 3,5-di-hydrocarbyl-4-hydroxylbenzyl groups, on the same basis. In some embodiments, the antioxidant products of the present invention comprise greater than 15 wt. %, in some embodiments greater than about 20 wt. % of heterocyclic compounds substituted with three 3,5-di-hydrocarbyl-4-hydroxylbenzyl groups, in other embodiments, greater than about 40 wt. %, of heterocyclic compounds substituted with four 3,5-di-hydrocarbyl-4-hydroxylbenzyl groups and heterocyclic compounds substituted with five 3,5-di-hydrocarbyl-4-hydroxylbenzyl groups, all based on the total weight of the antioxidant product. In the above embodiments, the antioxidant products of the present invention contain in the range of from about 1 to about 20 wt. %, preferably in the range of from about 1 to about 15 wt. %, and most preferably in the range of about 1 to 10 wt % of one or more methylene-bridged heterocyclic compounds substituted with one or more 3,5-di-hydrocarbyl-4-hydroxylbenzyl groups, all based on the total weight of the antioxidant product.
[0010] In some embodiments, the antioxidant products of the present invention can be described as comprising i) less than about 10 wt. %; preferably less than about 5 wt. %, more preferably less than about 1 wt. %, heterocyclic compounds substituted with one 3,5-di-hydrocarbyl-4-hydroxylbenzyl groups, all based on the total weight of the antioxidant product; ii) less than about 20 wt. %; preferably less than about 15 wt. %, more preferably less than about 10 wt. %, heterocyclic compounds substituted with two 3,5-di-hydrocarbyl-4-hydroxylbenzyl groups, all based on the total weight of the antioxidant product; iii) in the range of from about 15 wt. % to about 40 wt. %, preferably in the range of from about 15 wt. % to about 30 wt. %, more preferably in the range of from about 10 wt % to about 20 wt. % heterocyclic compounds substituted with three 3,5-di-hydrocarbyl-4-hydroxylbenzyl groups, on the same basis; iv) in the range of from about 10 wt % to about 70 wt. %, preferably in the range of from about 15 wt % to about 65 wt. %, more preferably in the range of from about 20 wt % to about 60 wt. % heterocyclic compounds substituted with four 3,5-di-hydrocarbyl-4-hydroxylbenzyl groups, on the same basis; v) in the range of from about 5 wt % to about 45 wt. %, preferably in the range of from about 8 wt % to about 40 wt. %, more preferably in the range of from about 10 wt % to about 35 wt. % heterocyclic compounds substituted with five 3,5-di-hydrocarbyl-4-hydroxylbenzyl groups, on the same basis; and vi) in the range of from about lwt % to about 15 wt. %, preferably in the range of from about 1 to about 10 wt. % of one or more methylene-bridged heterocyclic compounds substituted with one or more, in some embodiments in the range of from about 1 to about 12, 3,5-di-hydrocarbyl-4-hydroxylbenzyl groups, all based on the total weight of the antioxidant product.
[0011] In some embodiments, the reaction products comprise one or more compounds represented generally by Formula I:
[0000]
[0012] wherein X is sulfur, oxygen, or nitrogen, R 2 is H or hydrocarbyl, R 3 is 3,5-dihydrocarbyl-4-hydroxybenzyl, R 1 is H or hydrocarbyl, n is a whole number in the range of from about 0 to about 1, p is a whole number in the range of from about 1 to about 10, and m is 1 when n=0 and m is a whole number in the range of from about 2 to about 10 when n=1. In some embodiments, R1 is H, n=0, m=1, and p=1 and the reaction products of the present invention can be represented by Formula II:
[0000]
[0013] In some embodiments, X is sulfur, in some embodiments, X is oxygen, and in other embodiments, X is nitrogen.
[0014] As can be readily understood when discussing the degree of alkylation of the heterocyclic compounds in the reaction products of the present invention, the inventors hereof are referring to the “p” value. For example, if the reaction product is represented by the Formula I, a mono-alkylated heterocyclic compound would have a “p” value of 1 and be
[0015] represented generally by Formula III,
[0000]
[0016] In Formula III, R and R′ are independently H or hydrocarbyl, and R1 and X are as described above.
[0017] In some embodiments, the macromolecular antioxidant compositions of the present invention contain one or more, preferably two or more, compounds represented by the following general Formula IV:
[0000]
[0018] wherein R, R′, R1, R2 and R4 are independently hydrogen or hydrocarbyl, q and s are whole numbers and q+s=p, and X is as described above. For example, a tetra-alkylated methylene-bridged compound represented by Formula IV may be represented by Formula V:
[0000]
[0019] It is also obvious to the skilled in the art that the substitution pattern shown in Formulas II, III, IV, and V is for visual representation only and the alkyl and phenolic substitutions may take place on all the available active sites on the heterocyclic molecule. The skilled artisan will also recognize that in case of nitrogen containing heterocycles, it is possible to bridge through the nitrogen atom and in such cases the degree of alkylation will be two units higher than the thiophene analogs.
[0020] The antioxidant products of this invention, such as those described above, preferably have boiling points at atmospheric pressure of at least about 175° C.
Use of Reaction Products of the Present Invention
[0021] The reaction products of the present invention can be made available for use or sale as “neat” or as solutions in base oil compositions for use as an antioxidant in any organic substrate material normally susceptible to oxidative deterioration in the presence of air or oxygen. In this usage, an antioxidant quantity of a novel product of this invention can be blended with the substrate such as, for example, a lubricating oil; a liquid fuel; a thermoplastic polymer, resin or oligomer; or a natural or synthetic rubber or elastomer.
[0022] Additive compositions of this invention constitute another way of protecting such organic material against premature oxidative deterioration in the presence of air or oxygen. Thus, when adapted for use as an additive in oils, one or more reaction products of this invention can be partially diluted or dissolved in a base oil or process oil, or can be blended with other components that are commonly used in a wide variety of lubricants. Examples of base oils that may be used include Group I, II, and III mineral oils, poly-alpha-olefins, synthetic esters, gas to liquid derived oils and bio-based oils. Examples of other additives that may be used to produce new and useful lubricant additive blends with the reaction products of the invention include, but are not limited to, dispersants, detergents, anti-wear additives, extreme pressure additives, corrosion inhibitors, rust inhibitors, friction modifiers, pour point depressants, viscosity index modifiers, emulsifiers, demulsifiers, seal swell agents, solubilizing agents, antifoam agents, acid scavengers, metal deactivators, and other antioxidants or stabilizers. Combinations of one or more of these components can be used to produce additive blends with one or more of the reaction products of this invention. Also, additive compositions for use in internal combustion engine oils, railroad and marine lubricants, natural gas engine oils, gas turbine oils, steam turbine oils, aviation turbine oils, rust and oxidation oils, hydraulic fluids, compressor fluids, slideway oils, quench oils, manual and automatic transmission fluids, gear oils, greases, etc. can be formed by blending one or more of the reaction products of this invention with a diluent, solvent, or carrier fluid and/or one or more other suitable additives. The additive compositions of this invention adapted for use in oils can contain in the range of 5 wt % to 95 wt % depending upon the number and type of other components in the blend, based on the total weight of the additive composition. Finished lubricating oils of this invention will contain an antioxidant quantity of a product of this invention, which amount typically is at least about 0.1 wt %, preferably at least about 1 wt %, and more preferably at least about 3 wt % based on the total weight of the finished lubricating oil. Depending upon the type of service for which the oil of lubricating viscosity is intended, the amount of the product of this invention blended therein either as a sole additive or as an additive composition containing one or more other components will typically be no more than about 15 wt %, on the same basis.
[0023] The lubricating oil used in these embodiments of the present invention can be mineral, synthetic, or a blend of mineral and/or synthetic lubricating oils. These oils are typical industrial or crankcase lubrication oils for gas or steam turbines, transmission or hydraulic fluids, spark-ignited and compression-ignited internal combustion engines, for example natural gas engines, automobile and truck engines, marine, and railroad diesel engines. Mineral lubricating oils can be refined from aromatic, asphaltic, naphthenic, paraffinic or mixed base crudes. The lubricating oils can be distillate or residual lubricating oils, such as for example, bright stock, or blends of the oils to give a finished base stock of desired properties. Synthetic base oils used can be (i) alkyl esters of dicarboxylic acids, polyglycols and alcohols, (ii) poly-alpha-olefins, including polybutenes, (iii) alkyl benzenes, (iv) organic esters of phosphoric acids, or (v) polysilicone oils. The base oil typically has a viscosity of about 2 to about 15 cSt and preferably about 2.5 to about 11 cSt at 100° C.
[0024] Additive compositions adapted for use in forming liquid fuel compositions of this invention (e.g., gasolines, diesel fuels, jet fuels, gas turbine engine fuels, etc.) can be formed by blending therewith or providing therein an antioxidant quantity of one or more of the reaction products of this invention in the form of an additive composition of this invention comprising at least one novel compound of this invention together with one or more other additives, such as detergents, carrier fluids, demulsifiers, corrosion inhibitors, metal deactivators, lubricity agents, pour point depressants, cetane or octane improvers, antiknock agents, anti-icing agents, etc. The substrate fuels can be derived from petroleum or can be synthetic fuels, or they can be blends of both such types of materials. The amount of these new compositions in an additive blend of this invention can vary from 5 wt % to 95 wt %, based on the total weight of the additive blend, depending on the type and number of other components in the blend.
[0025] Liquid fuel compositions of this invention are typically formed by blending an antioxidant quantity of at least one of the reaction products of this invention with the fuel, either as a single additive composition (i.e., containing no other type(s) of fuel additive) or as an additive concentrate comprised of at least one of the reaction products of this invention together with at least one other type of fuel additive. The additive concentrates of this invention thus can contain in the range of about 5 to about 95 wt % of at least one of the reaction products of this invention, with the balance to 100 wt % being one or more other additives and optionally, a diluent, solvent or carrier fluid, all based on the total weight of the additive concentrate. The finished fuel compositions typically contain an antioxidant quantity in the range of about 0.0001 to about 0.1 wt %, and preferably in the range of about 0.001 to about 0.05 wt % of at least one of the reaction products of this invention, all based on the total weight of the finished fuel composition.
[0026] It will of course be understood that on blending one or more of the reaction products of this invention with a liquid substrate fuel or oil, the reaction products of this invention may no longer exist in exactly the same composition and form as they were upon addition to such substrate fuel or oil. For example, they may interact with one or more of the other components in the fuel or oil and/or they may complex with or otherwise change by virtue of becoming dissolved in the substrate fuel or oil. However, since the finished fuel or lubricant possess antioxidant properties because of the addition thereto of the one or more reaction products of this invention, the possibility of such transformations upon dilution in the substrate matters not. What matters pursuant to this invention is that whatever is formed upon such dilution is effective as an antioxidant. Consequently, expressions such as “containing in the range of”, “in”, etc. with reference to at least one of the reaction products of this invention are to be understood as referring to the at least one of the reaction products of this invention as it existed just prior to being blended or mixed with any liquid fuel or base oil and/or with any other component.
[0027] It will also be understood that the amount of the reaction products of this invention in a finished lubricant will vary depending upon the lubricant type, the identity of the one or more reaction products of this invention being used, and the desired level of performance required. For example, in a turbine oil, levels of the reaction product(s) of this invention often vary from about 0.05 to about 1.0 wt %, based on the total weight of the finished turbine oil. However, in an engine oil, levels typically vary from about 0.2 to about 2 wt % based on the total weight of the engine oil. In low phosphorus engine oils, levels may vary from about 0.3 to about 3 wt %, based on the total weight of the low phosphorus engine oil. In phosphorus-free engine oils levels may be as high as about 4 or 5 wt %, based on the total weight of the phosphorus-free engine oil. It will be understood that all wt. % are based on the total weight of the finished oil containing all additives, etc. When used properly the reaction products of this invention serve as antioxidant compositions. Thus, this invention also provides novel improved methods of reducing oxidation, reducing viscosity increase and polymerization, reducing acid formation and retaining lubricant basicity (TAN and TBN), reducing varnish and deposit formation, reducing friction and wear, reducing dependence on ZDDP and phosphorus for oxidation and deposit control, extending the usable life of all lubricant mentioned above, and reducing oil changes and vehicle maintenance. In each of such methods, a lubricant composition of this invention comprising an oil of lubricating viscosity with which has been blended an antioxidant quantity of at least one novel product of this invention is utilized as the lubricant. Still another method of this invention is a method of improving the oxidation stability of a lubricating oil, wherein said method comprises blending with a lubricating oil an oxidation stability improving amount of at least one reaction product of this invention. In this way the oxidation stability of the oil is significantly improved, as compared to the same oil except devoid of a reaction product of this invention.
[0028] An example of an engine oil composition of this invention is formed by blending together components that comprise:
Detergent: 0.5 to 5.0 wt % as pure component or concentrate. Concentrates typically contain 25 to 90 wt % diluent oil; Dispersant: 1.0 to 10.0 wt % as pure component or concentrate. Concentrates typically contain 25 to 90 wt % diluent oil; Zinc dialkyldithiophosphate (ZDDP): 0.1 to 1.5 wt % as pure component (with the lower amounts being preferred); Viscosity Modifier as an optional component: 1.0 to 15.0 wt % as pure component or concentrate. Concentrates typically contain 5 to 50 wt % diluent oil; Additional antioxidant(s) as one or more additional optional components: 0.01 to 1.0 wt % as pure component or concentrate. Concentrates typically contain 25 to 90 wt % diluent oil; Additional additives as one or more optional components used in amounts sufficient to provide the intended function of the additive(s): one or more friction modifiers, supplemental anti-wear additives, anti-foam agents, seal swell agents, emulsifiers, demulsifiers, extreme pressure additives, corrosion inhibitors, acid scavengers, metal deactivators, and/or rust inhibitors; At least one product of this invention: 0.1-2.5 wt %; with the balance to 100 wt % composed of one or more base oils.
[0036] It will be understood that all wt. % are based on the total weight of the finished oil containing all additives, etc.
[0037] Also provided by this invention are novel compositions comprised of at least one reaction product of this invention combined with:
1) at least one conventional hindered phenolic antioxidant 2) at least one conventional alkylated diphenylamine antioxidant 3) at least one organomolybdenum compound 4) at least one alkylated diphenylamine and at least one organomolybdenum compound 5) at least one phosphorus-free anti-wear or extreme pressure additive 6) at least one molybdenum-containing or boron-containing dispersant 7) at least one organoboron compound 8) at least one organoboron compound and at least one conventional alkylated diphenylamine 9) at least one sulfurized antioxidant, EP (extreme pressure) additive or anti-wear additive 10) at least one conventional alkylated diphenylamine along with at least one (i) sulfurized antioxidant, (ii) EP additive, (iii) anti-wear additive, and (iv) organoboron compound. 11) at least one base oil or process oil.
It will be understood, that it is within the scope of the present invention, that the compositions described in this paragraph can contain any one of 1)-11) or combinations of any two or more of 1)-11).
Processes for Forming the Products of the Invention
[0049] The macromolecular reaction products of the present invention can be formed by, for example, using process technology comprising bringing together to form a reaction mixture, components comprising:
(A) a sterically hindered 4-alkoxymethyl-2,6-dihydrocarbylphenol, preferably a sterically hindered 4-alkoxymethyl-2,6-dialkylphenol and more preferably, a 4-alkoxymethyl-2,6-di-tert-butylphenol in which the alkoxymethyl group is ethoxymethyl or methoxymethyl, and still more preferably,4-methoxymethyl-2,6-di-tert-butylphenol; or a sterically hindered 4-hydroxymethyl-2,6-dihydrocarbylphenol, preferably a sterically hindered 4-hydroxymethyl-2,6-dialkylphenol, and more preferably a 4-hydroxymethyl-2,6-di-tert-butylphenol and; (B) at least one heterocyclic compound which is a monocyclic or polycyclic compound wherein:
a) the monocyclic group of the monocyclic compound is fully conjugated and has as the sole heteroatom(s) in the fully conjugated ring thereof (i) one nitrogen atom, one sulfur atom, or one oxygen atom, (ii) one sulfur and one nitrogen atom, one sulfur and one oxygen atom, or one nitrogen and one oxygen atom, or (iii) two nitrogen atoms, two sulfur atoms, or two oxygen atoms, and b) at least one of the cyclic groups of the polycyclic compound is fully conjugated and has as the sole heteroatom(s) in the fully conjugated ring thereof (i) one nitrogen atom, one sulfur atom, or one oxygen atom, (ii) one sulfur and one nitrogen atom, one sulfur and one oxygen atom, or one nitrogen and one oxygen atom, or (iii) two nitrogen atoms, or two sulfur atoms, or two oxygen atoms;
(C) an alkylation catalyst, and (D) optionally, an organic solvent,
[0056] such that said at least one heterocyclic compound is alkylated to form a reaction product mixture between at least one component of (A) and at least one component of (B), with co-formation of or at least one alcohol, ROH, where RO corresponds to the alkoxy group or water. Various relative proportions of (A) and (B) can be used, whereby there is a molar excess of (A) relative to (B). In preferred embodiments, (A) and (B) are used in a molar ratio of (A) to (B) in the range of about 1:1 to about 10:1, more preferably 1:1 to about 7:1.
Component (A)
[0057] The sterically hindered 4-alkoxymethyl-2,6-dihydrocarbylphenol or 4-hydroxymethyl-2,6-dihydrocarbylphenol, used as a reactant to produce the antioxidant products of this invention can be any of a relatively large group of compounds. The hydrocarbyl groups in the ortho positions relative to the carbon atom carrying the hydroxyl group can be any univalent hydrocarbon group with the proviso that the resultant substitution in the 2- and 6-positions provides steric hindrance to the hydroxyl group. Typically, a total of at least 4 or 5 carbon atoms in the ortho positions is required to achieve steric hindrance. Among suitable hydrocarbyl groups that can be in the ortho positions are alkyl, cycloalkyl, alkenyl, cycloalkenyl, cycloalkylalkyl, aryl, and aralkyl in which the cyclic moieties, whether saturated or unsaturated, can in turn be alkyl substituted. The alkyl and alkenyl groups can be linear or branched. The individual hydrocarbyl groups in the ortho positions can each contain in the range of 1 to about 12 carbon atoms with the total number of carbon atoms in the ortho positions being in the range of about 4 to about 18 carbon atoms and preferably in the range of 8 to about 16 carbon atoms. 4-Alkoxymethylphenols in which at least one of the ortho positions is substituted by a tertiary alkyl group are preferred. The alkoxy group can be linear or branched and can contain up to about 18 carbon atoms and preferably up to about 6 carbon atoms. Preferred are the 4-alkoxymethyl hindered phenols in which the alkoxy group is ethoxy, and more preferably where the alkoxy group is methoxy. Branching of alkyl or alkenyl groups can occur anywhere in the alkyl or alkenyl group, including on the alpha-carbon atom of a secondary alkyl group such as isopropyl or sec-butyl, or on more remote positions such as on the beta-position in 2-ethylhexyl. Also, there can be any number of branches in the alkyl or alkenyl group, such as, for example, the four branches in a 1,1,3,3-tetramethylbutyl group.
[0058] Non-limiting examples of suitable sterically hindered 4-alkoxymethyl-2,6-dihydrocarbylphenols include, 4-ethoxymethyl-2,6-diisopropylphenol, 4-methoxymethyl-2-tert-butyl-6-methylphenol, 4-butoxymethyl-2,6-di-tert-butylphenol, 4-hexadecyloxymethyl-2-tert-butyl-6-methylphenol, 4-decyloxymethyl-2-tert-butyl-6-isopropylphenol, 4-hexyloxymethyl-2-cyclohexyl-6-ethylphenol, 4-methoxymethyl-2-tert-butyl-6-phenylphenol, 4-propoxymethyl-2-benzyl-6-isopropylphenol, 4-ethoxymethyl-2,6-di-tert-butylphenol, 4-methoxymethyl-di-tert-butylphenol, 4-(2-ethylhexyloxymethyl)-2,6-di-tert-butylphenol, and analogous hindered phenolic compounds. A preferred sub-group of sterically hindered 4-alkoxymethyl-2,6-dialkylphenols are those in which one of the ortho alkyl groups is tert-butyl and the other is methyl or, more preferably, tert-butyl and in which the alkoxymethyl group has a total of 9 carbon atoms. Particularly preferred is 4-methoxymethyl-2-tert-butyl-6-methylphenol. In one exemplary embodiment, (A) is 4-methoxymethyl-2,6-di-tert-butylphenol.
[0059] Non-limiting examples of suitable sterically hindered 4-hydroxymethyl-2,6-dihydrocarbylphenols include, 4-hydroxymethyl-2,6-diisopropylphenol, 4-hydroxymethyl-2-tert-butyl-6-methylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, 4-hydroxymethyl-2-tert-butyl-6-methylphenol, 4-hydroxymethyl-2-tert-butyl-6-isopropylphenol, 4-hydroxymethyl-2-cyclohexyl-6-ethylphenol, 4-hydroxymethyl-2-tert-butyl-6-phenylphenol, 4-hydroxymethyl-2-benzyl-6-isopropylphenol, 4-hydroxymethyl-2,6-di-tert-butylphenol, and analogous hindered phenolic compounds. A preferred sub-group of sterically hindered 4-hydroxymethyl-2,6-dialkylphenols are those in which one of the ortho alkyl groups is tert-butyl and the other is methyl or, more preferably, tert-butyl. Particularly preferred is 4-hydroxymethyl-2-tert-butyl-6-methylphenol. In one exemplary embodiment, (A) is 4-hydroxymethyl-2,6-di-tert-butylphenol.
Component (B)
[0060] In the practice of the present invention, (B) can be any of a number of compounds such as those described above. However, (B) is typically selected from heterocyclic compounds which are monocyclic or polycyclic compounds wherein the monocyclic group or at least one of the cyclic groups of the polycyclic compound is fully conjugated and has as the sole heteroatom(s), (i) one nitrogen atom, or one sulfur atom, or one oxygen atom, (ii) one sulfur and one nitrogen atom, one sulfur and one oxygen atom, one nitrogen and one oxygen atom, or (iii) two nitrogen atoms, or two sulfur atoms, or two oxygen atoms in the fully conjugated ring. Non-limiting examples of such compounds include pyrrole, imidazole, pyrazole, pyridine, pyrimidine, pyrazine, phenazine, thiophene, 2-benzothiophene, dibenzothiophene, dithiine, benzodithiine, indole, quinoline, acridine, carbazole, oxazole, isoxazole, thiazole, and isothiazole, furan, 2-benzofuran, 1,4-dioxin, benzodioxin, dibenzodioxin, and dibenzofuran. The rings of such compounds can be substituted by one or more electron releasing groups such as hydroxy, mercapto, alkoxy, amino, monoalkylamino, dialkylamino, and/or hydrocarbyl groups provided that at least one replaceable activated hydrogen atom remains on the ring. Non-limiting examples of such substituted compounds include 2-methylpyrrole, 2-ethylpyrrole, 2-methylpyridine, 2,4-dimethylpyridine, 2,3-dimethylpyrazine, 2-ethylpyridine, 2-methylimidazole, 2-methylfuran, 2-ethylfuran, 2,3-dimethylfuran and similar alkylated (e.g., C 1-12 ) heterocyclic compounds of the types referred to above.
[0061] In some processes, (B) can be selected from:
(B1) at least one heterocyclic compound which is a monocyclic, dicyclic, tricyclic or tetracyclic compound wherein the cyclic group of the monocyclic compound or at least one of the cyclic groups of the dicyclic, tricyclic or tetracyclic compound is fully conjugated and has as the sole heteroatom(s) in the fully conjugated ring thereof (i) one nitrogen atom, one sulfur atom, or one oxygen atom, (ii) one sulfur and one nitrogen atom, one sulfur and one oxygen atom, or one nitrogen and one oxygen atom, or (iii) two nitrogen atoms, two sulfur atoms, or two oxygen atoms, wherein each of (B1) (a) has at least one replaceable hydrogen atom on a ring thereof, (b) is substituted by one or more branched chain alkyl groups each having in the range of 3 to about 24 carbon atoms and preferably, in the range of 4 to about 12 carbon atoms, and (c) optionally, has one or more additional alkyl side chains each having in the range of 1 to about 3 carbon atoms.
[0063] In some embodiments (B) can be selected from:
(B2) at least one heterocyclic compound which is a monocyclic, dicyclic, tricyclic or tetracyclic compound wherein the cyclic group of the monocyclic compound or at least one of the cyclic groups of the dicyclic, tricyclic or tetracyclic compound is fully conjugated and has as the sole heteroatom(s) in the fully conjugated ring thereof (i) one nitrogen atom, one sulfur atom, or one oxygen atom, (ii) one sulfur and one nitrogen atom, one sulfur and one oxygen atom, or one nitrogen and one oxygen atom, or (iii) two nitrogen atoms, two sulfur atoms, or two oxygen atoms;
[0065] wherein (B2) has (a) at least one replaceable hydrogen atom on a ring thereof, and (b) optionally, one or more alkyl side chains each having in the range of 1 to 2 carbon atoms.
Component (C)
[0066] In the processes described herein, an alkylation catalyst is used to promote the reaction between (A) and (B), thus the reaction between (A) and (B) is sometimes referred to as an alkylation reaction herein. The alkylation reaction catalyst used herein can be selected from any alkylation catalyst known to promote the reaction of (A) and (B). In some embodiments, (C) is preferably an acidic catalyst such as sulfuric acid, an aryl sulfonic acid, an alkyl sulfonic acid, or an aryl alkyl sulfonic acid. Non-limiting examples of other suitable alkylation catalysts include, for example, hydrochloric acid, hydrobromic acid, aluminum chloride, diethyl aluminum chloride, triethylaluminum/hydrogen chloride, ferric chloride, zinc chloride, antimony trichloride, stannic chloride, boron trifluoride, acidic zeolites, acidic clays, and polymeric sulfonic acids such as those sold under the name Amberlyst®.
Component (D)
[0067] The processes of the present invention are carried out in a liquid reaction medium that can result from one of the reactants being a liquid under the conditions of the alkylation reaction, or which can result from use of an inert organic solvent. Non-limiting examples of organic solvents which can be used include, for example, acetic acid, propionic acid, one or more hexane isomers, one or more heptane isomers, one or more octane isomers, one or more decanes, mixtures of one or more of the alkane solvents such as the foregoing, cyclohexane, methylcyclohexane, methylene dichloride, methylene dibromide, bromochloromethane, 1,2-dichloroethane, 1,2-dibromoethane, chloroform, chlorobenzene, mixtures of one or more chlorinated and/or brominated solvents such as the foregoing, and one or a mixture of alkanols such as methyl alcohol, ethyl alcohol, isopropyl alcohol, n-propyl alcohol, n-butyl alcohol, sec-butyl alcohol, isobutyl alcohol, 2-ethylhexyl alcohol, octyl alcohol, and other liquid or low melting homologous alkanols, and one or more ethers like dialkyl ethers, tetrahydrofuran, dioxane or mixtures thereof. In some embodiments, the solvent is a hydrocarbon solvent. In preferred embodiments, (D) is used in the practice of the present invention.
Process Conditions
[0068] The processes described herein are conducted at one or more temperatures in the range of from about 20° C. to about 160° C. or higher. In some embodiments, the processes of the present invention are conducted at one or more temperatures above 40° C., preferably in the range of from 70° C. to about 160° C., or higher. The inventors hereof have discovered that reaction temperatures within these ranges are more suitable for producing the reaction products of the present invention. Further, the inventors hereof have discovered that at higher temperatures, i.e. greater than 40° C., the processes of the present invention proceed more rapidly and thus completion can be reached in shorter periods of time than previously contemplated. For example, when 2,6-di-tert-butyl-4-methoxymethylphenol is used as (A), the reaction tends to initiate relatively rapidly at room temperature, (about 23° C.) until about one equivalent of the 2,6-di-tert-butyl-4-methoxymethylphenol has been consumed. Thereafter, the reaction tends to proceed more slowly and consequently additional heat energy needs to be applied and/or additional catalyst employed. However, at higher temperatures, i.e. greater than 40° C., this reaction proceeds more rapidly and thus completion can be reached in shorter periods of time.
[0069] With lower boiling reactants and/or solvents the reaction may be conducted under pressure, or the reaction may be conducted in the presence of a cooling condenser. In most cases, the reaction results in alkylation on an activated, electron rich ring. In some cases, alkylation may occur on a nitrogen atom.
[0070] In the practice of the present invention, the inventors hereof have discovered that by varying the relative molar ratio of (A) to (B), one can produce various macromolecular reaction products, as described below, that find use as antioxidants. In some embodiments, (A) and (B) are used in a molar ratio of (B) to (A) in the range of about 1:1 to about 1:10, preferably in the range of from about 1:1 to about 1:7, in some embodiments, the molar ratio of (B) to (A) in the range of about 1:3 to about 1:10, preferably in the range of from about 1:3 to about 1:7. In preferred embodiments, the molar ratio of (B) to (A) can be any of about 1:1, about 1:2, about 1:2.5, about 1:3, about 1:3.5, about 1:4, about 1:4.5, about 1:5, about 1:5.5, about 1:6, about 1:6.5, or about 1:7.
[0071] The above description is directed to several embodiments of the present invention. Those skilled in the art will recognize that other means, which are equally effective, could be devised for carrying out the spirit of this invention. It should also be noted that preferred embodiments of the present invention contemplate that all ranges discussed herein include ranges from any lower amount to any higher amount.
[0072] The following examples will illustrate the present invention, but are not meant to be limiting in any manner.
EXAMPLES
[0073] The antioxidant effectiveness of the products in the following examples was analyzed by use of a standardized oxidation test procedure (ASTM D 6186) in which a lubricating oil containing a specified amount of an additive is subjected to oxidation in a heated pressure-resistant vessel at a temperature of 160° C. charged with oxygen under an initial elevated pressure of 500 psig. The longer the induction time (OIT) before a pressure drop occurs, the more stable the composition.
Example 1
Thiophene and 2,6-di-tert-butyl-4-methoxymethylphenol (1:1 Ratio)
[0074] A three-necked round-bottomed flask was equipped with an addition funnel, magnetic stirrer, temperature probe, and a condenser. Thiophene (0.1 mol, 8.4 g) was dissolved in dichloromenthane (20 mL) and sulfuric acid (3 mL of 80%) was added at room temperature. A solution of 2,6-di-tert-butyl-4-methoxymethylphenol (0.1 mol, 25 g) in dichloromethane (50 mL) was added at room temperature and in small increments. An exothermic reaction ensued during the addition of the first equivalent of 2,6-di-tert-butyl-4-methoxymethylphenol, but it subsided when the addition continued. The reaction mixture was stirred at room temperature for 3 hrs. NMR Analysis showed complete conversion of the starting materials. The acid phase was separated and the organic phase was washed with water (20 mL), dilute sodium hydroxide to pH 7-8, water (20 mL), and dried over magnesium sulfate. Evaporation of solvent under reduced pressure afforded a viscose oil which solidified on standing at room temperature, mp 54° C. HPLC Analysis showed mono-substituted isomer (13%), di-substituted isomer (18%), tri-substituted isomer (19%), tetra-substituted isomer (32%), and penta-substituted isomer (11%). In addition 6% of methylene-bridged products and other oligomeric materials were identified in the product. Oxidation Inhibition Time measured by PDSC @ 160° C. was 72 minutes at 0.25 wt %%, 115 minutes at 0.50% wt %, and 174 minutes at 0.75 wt % loading.
Example 2
Thiophene and 2,6-di-tert-butyl-4-methoxymethylphenol (1:2ratio)
[0075] A three-necked round-bottomed flask was equipped with an addition funnel, magnetic stirrer, temperature probe, and a condenser. Thiophene (0.1 mol, 8.4g) was dissolved in dichloromenthane (20 mL) and sulfuric acid (3 mL of 80%) was added at room temperature. A solution of 2,6-di-tert-butyl-4-methoxymethylphenol (0.2 mol, 50 g) in dichloromethane (60 mL) was added at room temperature and in small increments. An exothermic reaction ensued during the addition of the first equivalent of 2,6-di-tert-butyl-4-methoxymethylphenol, but it subsided when the addition continued. The reaction mixture was stirred at room temperature for 3 hrs. NMR Analysis showed complete conversion of the starting materials. The acid phase was separated and the organic phase was washed with water (20 mL), dilute sodium hydroxide to pH 7-8, water (20 mL), and dried over magnesium sulfate. Evaporation of solvent under reduced pressure afforded a viscose oil which solidified on standing at room temperature. The solid did not have a clear melting point but became fluid at 70° C. HPLC Analysis showed mono-substituted isomer (5%), di-substituted isomer (8%), tri-substituted isomer (13%), tetra-substituted isomer (40%), penta-substituted isomer (20%). In addition 12% of methylene-bridged products and other oligomeric materials were identified in the product. Oxidation Inhibition Time measured by PDSC @ 160° C. was 68 minutes at 0.25 wt %%, 114 minutes at 0.50% wt %, and 169 minutes at 0.75 wt % loading.
Example 3
Thiophene and 2,6-di-tert-butyl-4-methoxymethylphenol (1:2.4) ratio)
[0076] The same procedure as example 1 was used, except a thiophene/2,6-di-tert-butyl-4-methoxymethylphenol mole ratio of 1:2.4 was used. A solid product, mp 71° C., was isolated. HPLC Analysis showed mono-substituted isomer (1%), di-substituted isomer (4%), tri-substituted isomer (20%), tetra-substituted isomer (59%), penta-substituted isomer (11%). In addition 4% of methylene-bridged products and other oligomeric materials were identified in the product. Oxidation Inhibition Time measured by PDSC @ 160° C. was 72 minutes at 0.25 wt %%, 124 minutes at 0.50% wt %, and 187 minutes at 0.75 wt % loading.
Example 4
Thiophene and 2,6-di-tert-butyl-4-methoxymethylphenol (1:3ratio)
[0077] The same procedure as example 1 was used, except a thiophene/2,6-di-tert-butyl-4-methoxymethylphenol mole ratio of 1:3 was used. A solid product, mp 53° C., was isolated. HPLC Analysis showed mono-substituted isomer (3%), di-substituted isomer (5%), tri-substituted isomer (13%), tetra-substituted isomer (34%), penta-substituted isomer (28%). In addition 13% of methylene-bridged products and other oligomeric materials were identified in the product. Oxidation Inhibition Time measured by PDSC @ 160° C. was 72 minutes at 0.25 wt %%, 124 minutes at 0.50% wt %, and 187 minutes at 0.75 wt % loading.
Example 5
Thiophene and 2,6-di-tert-butyl-4-methoxymethylphenol (1:2 ratio) in toluene
[0078] A three-necked round-bottomed flask was equipped with an addition funnel, magnetic stirrer, temperature probe, and a condenser. Thiophene (0.1 mol, 8.4 g) was dissolved in toluene (40 mL) and sulfuric acid (6 mL of 80%) was added at room temperature. A solution of 2,6-di-tert-butyl-4-methoxymethylphenol (0.2 mol, 50 g) in toluene (170 mL) was added at 50° C. over 45 minutes. The reaction mixture was heated to 110° C. and was refluxed for 3 hrs. NMR analysis showed complete conversion of the starting material. The acid phase was separated and the organic phase was washed with water (30 mL), dilute sodium hydroxide to pH 7-8, water (30 mL), and dried over magnesium sulfate. Evaporation of solvent under reduced pressure afforded a viscose oil which solidified on standing at room temperature. HPLC Analysis showed mono-substituted isomer (21%), di-substituted isomer (34%), tri-substituted isomer (25%), tetra-substituted isomer (9%), penta-substituted isomer (10%). In addition 10% of methylene-bridged products and other oligomeric materials were identified in the product. Oxidation Inhibition Time measured by PDSC @ 160° C. was 84 minutes at 0.25 wt %%, 131 minutes at 0.50% wt %, and 184 minutes at 0.75 wt % loading.
Example 6
Thiophene and 2,6-di-tert-butyl-4-methoxymethylphenol (1:3 ratio) in toluene
[0079] A three-necked round-bottomed flask was equipped with an addition funnel, magnetic stirrer, temperature probe, and a condenser. Thiophene (0.1 mol, 8.4 g) was dissolved in toluene (40 mL) and sulfuric acid (6 mL of 80%) was added at room temperature. A solution of 2,6-di-tert-butyl-4-methoxymethylphenol (0.3 mol, 75 g) in toluene (230 mL) was added at 50° C. over one hour. The reaction mixture was heated to 110° C. and was refluxed for 3 hrs. NMR analysis showed complete conversion of the starting material. The acid phase was separated and the organic phase was washed with water (30 mL), dilute sodium hydroxide to pH 7-8, water (30 mL), and dried over magnesium sulfate. Evaporation of solvent under reduced pressure afforded a viscose oil which solidified on standing at room temperature. HPLC Analysis showed mono-substituted isomer (7%), di-substituted isomer (21%), tri-substituted isomer (29%), tetra-substituted isomer (19%), penta-substituted isomer (4%). In addition 16% of methylene-bridged products and other oligomeric materials were identified in the product.
Example 7
Thiophene and 2,6-di-tert-butyl-4-methoxymethylphenol (No Solvent)
[0080] A solution of 2,6-di-tert-butyl-4-methoxymethylphenol (5 g) in thiophene (20 mL) was added to a stirred mixture of sulphuric acid (0.5 mL of 80%) and thiophene (10 mL) at room temperature. The reaction mixture was stirred at room temperature overnight. NMR analysis showed complete conversion of the starting material. The acid phase was removed and the crude reaction mixture was diluted with dichloromethane (20 mL) and it was washed with water (10 mL) and dried over magnesium sulfate. Solvent was removed under aspirator pressure followed by distillation of excess thiophene at 1-2 mmHg and 60° C. The product was an orange oil at room temperature. HPLC analysis showed mono-substituted product (91%), and di-substituted product (2%). In addition 6% of methylene-bridged products and other oligomeric materials were identified in the product.
Example 8
Thiophene and 2,6-di-tert-butyl-4-methoxymethylphenol (No Solvent with Amberlyst® Catalyst)
[0081] To a solution of 2,6-di-tert-butyl-4-methoxymethylphenol (15 g) in thiophene (50 mL) was added Amberlyst® 35 and the resulting mixture was refluxed for 23 hrs. NMR Analysis showed complete conversion of the starting material. After cooling to room temperature, the reaction mixture was filtered and the filtrate was concentrated as described in example 7. HPLC analysis of the resulting oil showed mono-substituted product (70%), di-substituted product (21%), and tri-substituted product (3%). In addition 6% of methylene-bridged products and other oligomeric materials were identified in the product. Oxidation Inhibition Time measured by PDSC @ 160° C. was 87 minutes at 0.25 wt %%, 119 minutes at 0.50% wt %, and 157 minutes at 0.75 wt % loading.
Example 9
Furan and 2,6-di-tert-butyl-4-methoxymethylphenol (1:3 ratio)
[0082] A three-necked round-bottomed flask was equipped with an addition funnel, magnetic stirrer, temperature probe, and a condenser. A solution of furan (0.1 mol, 6.8 g) in dichloromethane (20 mL) was added to a solution of 2,6-di-tert-butyl-4-methoxymethylphenol (0.3 mol, 75 g) in dichloromethane (200 mL) and sulphuric acid (3 mL of 80%) at room temperature over about 10 minutes. The reaction mixture was first stirred at room temperature overnight and refluxed for 4 hrs. NMR analysis showed complete conversion of the starting material. The acid phase was separated and the organic phase was washed with water (30 mL), dilute sodium hydroxide to pH 7-8, water (30 mL), and dried over magnesium sulfate. Evaporation of solvent under reduced pressure afforded a viscose oil which solidified on standing at room temperature. HPLC Analysis showed mono-substituted isomer (3%) and di-substituted isomer (15%). In addition about 80% of methylene-bridged products and other oligomeric materials were identified in the product. Oxidation Inhibition Time measured by PDSC @ 160° C. was 57 minutes at 0.25 wt %%, 69 minutes at 0.50% wt %, and 78 minutes at 0.75 wt % loading.
Example 10
Furan and 2,6-di-tert-butyl-4-methoxymethylphenol (No Solvent)
[0083] A three-necked round-bottomed flask was equipped with an addition funnel, magnetic stirrer, temperature probe, and a condenser. A solution of 2,6-di-tert-butyl-4-methoxymethylphenol (25 g) in furan (100 L) was added to a stirred mixture of furan (50 mL) and sulphuric acid (5 mL of 80%) in 15 minutes. The reaction mixture was stirred at room temperature for 3 hrs. Then it was filtered through a short Celite bed and the filtrate was concentrated under reduced pressure. The oily residue was dissolved in hexanes (60 mL) and the resulting solution was washed with water (30 mL), dilute sodium hydroxide to pH 7-8, water (30 mL), and dried over magnesium sulfate. Evaporation of solvent under reduced pressure afforded a viscose oil which solidified on standing at room temperature. HPLC Analysis showed mono-substituted isomer as the major product (91%). Oxidation Inhibition Time measured by PDSC @ 160° C. was 53 minutes at 0.25 wt %%, 63 minutes at 0.50% wt %, and 69 minutes at 0.75 wt % loading. | This invention relates to novel macromolecular compositions having oxidation inhibition characteristics that are exhibited when added to organic material normally susceptible to oxidative degradation in the presence of air or oxygen, such a petroleum products, synthetic polymers, and elastomeric substances. | 2 |
REFERENCE TO PROVISIONAL APPLICATION
This application is based on, claims priority to, and hereby refers to U.S. Provisional Patent Application Ser. No. 61/192,927, filed Sep. 23, 2008, entitled “Fluid Powered Motor and Pump,” the entire contents of which are incorporated herein by this reference.
FIELD OF THE INVENTION
This invention relates to fluid-powered motors and pumps and more particularly, but not necessarily exclusively, to motors and pumps powered by (or powering) liquids such as water. The motors and pumps may be especially useful in connection with filtration systems for pools and spas, although they may be used in other ways as well.
BACKGROUND OF THE INVENTION
U.S. Pat. No. 4,449,265 to Hoy illustrates an example of a wheeled automatic swimming pool cleaner. Powering the wheels is an impeller comprising an impeller member and pairs of vanes. Evacuating the impeller causes water within a swimming pool to interact with the vanes, rotating the impeller member. The impeller is reversible, with the impeller member apparently moving laterally when the pool cleaner reaches an edge of a pool to effect the rotation reversal.
U.S. Pat. No. 6,292,970 to Rief, et al., describes a turbine-driven automatic pool cleaner. The cleaner includes a turbine housing defining a water-flow chamber in which a rotor is positioned. Also included are a series of vanes pivotally connected to the rotor. Water interacting with the vanes rotates the rotor in one direction (clockwise as illustrated in the Rief patent), with the vanes pivoting when encountering “debris of substantial size” to allow the debris to pass through the housing for collection. The contents of the Hoy and Rief patents are incorporated herein in their entireties by this reference.
SUMMARY OF THE INVENTION
The present invention provides efficient alternatives to conventional impellers and turbines. The invention also may be activated as a pump and, if desired, may switch between motor and pump functions dynamically. It has especial usefulness as a motor powering an automatic swimming pool cleaner, although the invention may be utilized in connection with other aspects of a filtration system for a pool or spa or as part of any other system in which conversion of energy from, for example, a suction or pressure source to rotational power is necessary or desired.
Currently-preferred versions of the present invention typically comprise a body having at least one inlet and at least one outlet. Within the body are positioned one or more pairs of paddles whose distal edges may, if desired, be locally flexible to facilitate passage of debris. Such local flexibility is not required, however. Rather than being placed in the same plane (or otherwise uniformly formed), however, paddles of a pair in the present invention may be positioned perpendicularly. Stated differently, if the paddles themselves are generally planar and one paddle of a pair exists in a first plane, the other paddle of the pair may exist in a second plane normal to the first plane. In other versions these paddles of a pair need not necessarily be perpendicular to each other, although some angular difference between orientations of paddles of a pair may be beneficial. In yet other versions, paddles need not necessarily be paired, although again having angular differences between orientations of various paddles may be advantageous.
In at least one version of the invention having paired paddles, a first pair of paddles is connected by a shaft. The paddles additionally are connected, via hinges, bearings, or other connection means, to a base. The base is configured to allow some rotation of the paddles about an axis aligned with at least part of the shaft, with the base and connection means also functioning to limit rotation of the paddles in some, but not all, versions of the invention. Preferably, the paddles may rotate through an angle of ninety degrees about this axis, although other angular rotations may occur instead.
At least this embodiment further includes a second pair of paddles likewise connected by a shaft and to a base. Each of the two shafts beneficially may be non-linear, allowing the shafts to cross without interfering with paddle rotation yet permitting portions of each shaft to remain in the same plane. Moreover, the two bases may be configured to fit together, forming a unitary structure housing at least parts of both shafts. Either or both bases may include an outwardly-extending shaft that provides (1) rotational output when the invention is used as a motor and (2) rotational input when the invention is used as a pump.
Bodies consistent with the invention may be hollow (or have hollow portions) into which the paddles and bases are fitted. The unitary structure including the paddles and bases may rotate about the outwardly-extending shaft (or shafts) a full three hundred sixty degrees (i.e. in paddle-wheel fashion) either clockwise or counter-clockwise as desired. Consequently, paddles of the present invention may rotate about two different axes in operation, although they preferably do not move linearly—unlike the impeller member of the Hoy patent.
The bodies also may be configured to present flow restrictions. Such a restriction may, when contacted by a paddle, cause the paddle to rotate so that its faces are parallel (or generally parallel) to the fluid direction through the body. This rotation in turn causes the paired paddle to rotate so that its faces are perpendicular to the flow direction. The result is one paddle of a pair presenting minimum surface area to the flow direction while the other provides maximum surface are to the flow direction, allowing the suction or pressure force to work with greatest efficiency in rotating the unitary structure to supply high-torque output.
Stated differently, the present invention uses predominantly surface-area differentials to cause rotary motion. The fluid-flow pressure encountered by both paddles of a pair is the same (or approximately so); one paddle merely presents a larger surface area to the fluid flow than does the other paddle. This concept differs significantly from that of standard impellers, which jet fluid at one side of an impeller to cause a pressure differential on sides of the blades, thus creating rotation to relieve the imbalance.
Moreover, in standard impellers, a blade opposite the one being impacted by the jetted fluid is moving fluid in a direction opposite the flow. In this sense, it is “dragging dead fluid” along, reducing the overall efficiency of the device. By contrast, no material level of such “dragging” occurs in connection with the present invention.
It thus is an optional, non-exclusive object of the present invention to provide fluid-powered devices that may be employed as motors or pumps (or both).
It is another optional, non-exclusive object of the present invention to provide fluid-powered devices using, predominantly or exclusively, surface-area differentials to cause rotary motion.
It is a further optional, non-exclusive object of the present invention to provide fluid-powered devices utilizing at least one pair of paddles, with each paddle of a pair being non-planar, or otherwise non-uniformly oriented, with the other paddle of the pair.
It is, moreover, an optional, non-exclusive object of the present invention to provide paddles configured to rotate about multiple axes.
It is also an optional, non-exclusive object of the present invention to provide fluid-powered devices having a pair of paddles connected via a non-linear shaft.
It is an additional optional, non-exclusive object of the present invention to provide fluid-powered devices especially useful in connection with automatic swimming pool cleaners or other equipment used as part of filtration systems of pools, spas, or hot tubs.
Other objects, features, and advantages of the present invention will be apparent to those skilled in appropriate fields with reference to the remaining text and the drawings of this application.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a first exterior plan view of an exemplary device consistent with the present invention.
FIG. 2 is a second exterior plan view of the device of FIG. 1 .
FIG. 3 is a first perspective view of portions of the device of FIG. 1 , including two pairs of paddles and a flow restrictor depicted within a body.
FIG. 4 is a second perspective view of portions of the device of FIG. 1 , including the pairs of paddles of FIG. 3 .
FIG. 5 is a perspective view of the pairs of paddles of FIG. 3 .
DETAILED DESCRIPTION
Depicted in FIGS. 1-2 is exemplary device 10 . Device 10 may function as a motor or pump or as any other device configured to convert energy from a suction or pressure source to rotational movement. Device 10 may include body 14 defining inlet 18 and outlet 22 as well as outwardly-extending shafts 26 . Although two such outwardly-extending shafts 26 are illustrated in FIGS. 1-2 , more or fewer shafts 26 may be utilized instead. Likewise, although shafts 26 are shown in FIGS. 1-2 as being elongated rods, they may be configured or shaped differently than as shown.
Body 14 may, if desired, comprise at least first and second portions 30 and 34 . If so, first and second portions 30 and 34 preferably are connected in use, as illustrated in FIGS. 1-2 . At least part of body 14 additionally preferably (although not necessarily) is symmetric about both (1) the connection between first and second portions 30 and 34 and (2) an axis coincident with shafts 26 . Fluid flow through body 14 may occur from inlet 18 to outlet 22 or from outlet 22 to inlet 18 . Hence, the terms “inlet” and “outlet” of body 14 are used herein for convenience, as the “inlet” may at times be the outlet of body 14 and the “outlet” may at these times be the inlet of body 14 .
Also depicted in FIGS. 1-2 as being within body 14 is an exemplary blade, vane, or paddle 38 as well as restriction 42 and hubs or bases 46 A and 46 B. Paddle 38 , together with one or more similar paddles, may be connected directly or indirectly to outwardly-extending shafts 26 . When device 10 is employed as a motor, fluid flowing through body 14 interacts with each paddle 38 to produce rotation of shafts 26 .
FIGS. 3-5 depict multiple paddles 38 . FIG. 5 , in particular, illustrates that paddles 38 may, if desired, be paired; two such pairs are shown in the figure, with one pair comprising paddles 38 A and 38 B and the other pair comprising paddles 38 C and 38 D. In presently-preferred versions of device 10 , paddles 38 A and 38 B are connected by shaft 50 A and paddles 38 C and 38 D are connected by shaft 50 B. Preferably no direct connection exists between paddles 38 A and 38 B, on the one hand, and paddles 38 C and 38 D, on the other hand. Instead, shafts 50 A and 50 B are configured to cross in a manner avoiding interference by shaft 50 A with rotation of paddles 38 C and 38 D and by shaft 50 B with rotation of paddles 38 A and 38 B. Although device 10 preferably includes four paddles 38 (e.g. paddles 38 A, 38 B, 38 C, and 38 D), more or fewer paddles 38 may be used.
In a version of paddles 38 depicted in FIGS. 3-5 , shaft 50 A resembles an elongated cylinder and thus may define a generally longitudinal axis X. Shaft 50 B is similar, defining a generally longitudinal axis Y. Central portion 54 A of shaft 50 A, however, deviates from axis X, essentially being shifted laterally from the axis X to form nesting space 58 A. Likewise, central portion 54 B of shaft 50 B is translated from axis Y to form nesting space 58 B. Shaft 50 A thus may be placed generally in the same plane as shaft 50 B, with nesting spaces 58 A and 58 B being adjacent. In the version shown in FIG. 5 , central portion 54 A is atop central portion 54 B but not in contact therewith because of the alignment of nesting spaces 58 A and 58 B.
FIG. 5 additionally illustrates a preferred relative orientation of paddles 38 of a pair. Paddle 38 A, for example, is shown in FIG. 5 as having a principal face 62 (together with its opposite face, which is not shown) generally in the plane of the page. By contrast, paddle 38 B is depicted as having its principal and opposite face 66 (as well as its unshown opposite face) generally normal to the plane of the page. Stated differently, a plane containing principal face 62 and passing through axis X preferably is perpendicular to a plane containing principal face 66 and passing through axis X, so that principal faces 62 and 66 are offset by ninety degrees. Accordingly, when principal face 62 presents maximum surface area to the flow direction through body 14 , principal face 66 will present minimum surface area to the flow direction. Relative orientation of paddles 38 C and 38 D preferably is similar; a plane containing principal face 70 of paddle 38 D passing through axis Y may be perpendicular to a plane containing principal and opposite faces 74 and 78 , respectively, of paddle 38 C passing through the axis Y.
Although relative faces of pairs of paddles 38 preferably are offset by ninety degrees, this exact angular orientation is not mandatory. Angular offset should be greater than zero for paddles 38 of a pair; thus the invention contemplates any other such offset. Nevertheless, offsets greater than, for example, five, twenty, or forty-five degrees may be necessary to produce satisfactory results in many cases. Because preferred versions of shafts 50 A and 50 B and faces 62 , 66 , 70 , 74 , and 78 (etc.) are inflexible, paddles 38 A and 38 B will retain their angular offset at all times, while paddles 38 C and 38 D likewise will retain their angular offset at all times. If desired, however, paddle edges (such as edge 82 of paddle 38 A) may be flexible to facilitate passage of debris through body 14 or reduce frictional wear of paddles 38 (or of body 14 ).
Shafts 50 A and 50 B, together with bearings-containing wheels 86 , may be placed in base 46 B as illustrated in FIG. 3 . Base 46 A ( FIG. 4 ) may be fitted over wheels 86 and attached to base 46 A. The resulting structure permits shafts 50 A and 50 B and associated paddles 38 A-D to rotate about axis Z coincident with shafts 26 . When device 10 functions as a motor, rotation about axis Z occurs because of fluid flow through body 14 ; if fluid enters via inlet 18 , rotation will be in the direction of arrow A (see FIG. 3 ). Conversely, if fluid enters via outlet 22 , rotation will be in the opposite direction, as shown by arrow B. (Alternatively, restriction 42 may be repositioned appropriately within body 14 to reverse rotational direction without changing whether fluid enters via inlet 18 or outlet 22 .) Because shafts 26 are connected to the rotating components, they too will rotate, providing power available to perform useful work.
In use, paddles 38 rotate about another axis as well. Paddles 38 A-B, for example, may rotate about axis X, while paddles 38 C-D may rotate about axis Y. This second type of rotation is caused by restrictor 42 .
Assume, for example, that paddles 38 A-D are configured and oriented as shown in FIG. 3 and rotating in the direction of arrow A. Paddle 38 C is generally vertical in this example as it approaches restrictor 42 , which is shown as being in the form of a ramp. Further movement in the direction of arrow A causes face 78 of paddle 38 C to contact restrictor 42 , whose sloping surface 90 (see also FIG. 2 ) forces paddle 38 C to rotate about axis Y so as to reorient generally horizontally (with its face 74 ultimately facing upward like face 62 in FIG. 3 ). As paddle 38 C rotates from a generally vertical position to a generally horizontal one, paired paddle 38 D will rotate from a generally horizontal position to a generally vertical one. Indeed, this relationship is illustrated in FIG. 3 by paired paddles 38 A and 38 B: Paddle 38 A has already been forced by restrictor 42 into a generally horizontal orientation, causing paired paddle 38 B to assume a generally vertical orientation.
Continuing this example consistent with FIG. 3 , fluid entering inlet 18 may travel to outlet 22 via either side of base 46 B—i.e. through both channel 94 and channel 98 . (Preferably, however, channel 98 is substantially more restricted than channel 94 , so that only limited flow occurs therethrough.) The fluid entering inlet 18 initially encounters paddle 38 D. Because paddle 38 D is generally horizontal, it presents minimal surface area to the direction of fluid flow from inlet 18 to outlet 22 . This result additionally is true for paddle 38 A, having been forced to the horizontal position by restriction 42 (and in effect sealing, or substantially sealing, channel 98 ). By contrast, paddle 38 B is generally vertical, presenting maximum surface area (in the form of face 66 , which is not shown in FIG. 3 but is depicted in FIG. 5 ) to the fluid flow direction. This differential surface area causes the flowing fluid to push on paddle 38 B, resulting in paddle rotation in the direction of arrow A.
Although not illustrated in FIG. 3 , restrictor 42 may continue throughout channel 98 or otherwise have a sloping surface adjacent inlet 18 , so that device 10 may be operated in reverse. Further, if power is supplied to rotate one or more shafts 26 , the shafts 26 in turn may rotate paddles 38 about axis Z so that device 10 may function as a fluid pump, in this sense being fluid “powered” in its operation regardless of how shafts 26 are caused to rotate. As a consequence, device 10 provides a versatile, efficient mechanism for using flowing fluid to create rotation.
The foregoing is provided for purposes of illustrating, explaining, and describing embodiments of the present invention. Modifications and adaptations to these embodiments will be apparent to those skilled in the art and may be made without departing from the scope or spirit of the invention. | Fluid-powered devices are detailed. The devices may be utilized as motors or pumps, for example, and are capable to switching dynamically between these functions. They additionally may use surface-area, rather than solely pressure, differentials to produce rotary motion. | 5 |
FIELD OF THE INVENTION
[0001] The present invention relates to the use of materials as insecticides, nemotocides and molluscocides and specifically to the use of a concentrate obtained from garlic for these purposes.
REVIEW OF THE ART KNOWN TO THE APPLICANT
[0002] The European Union's review of pesticide active ingredients is expected to lead to the removal of over 66% of the presently approved active substances by 2007. There is therefore a need for new more environmentally friendly pesticides.
[0003] The use of garlic oil as a avian repellent has previously been reported by Eric Block et al in the Journal of Agricultural and Food Chemistry, Volume 5, No. 8, pages 2192 to 2196 (1). Garlic derived preparations showing insect repellent activity and the toxicity of garlic to mosquito and other insect larvae have also been reported, see E Block, et al, Angew Chem. Int. Ed. Engl. 1992, 31, 1135-1178 (2); Kadota, Y. Insect repellents made from plant and herb extracts, JP 2003192516, 2003 (Chem. Abstr. 2003, 139, 48654) (3); and Bhuyan, M.; Saxena, B. N.; Rao, K. M. Repellent Property of Oil Fraction of Garlic, Allium Sativum Linn. Ind. J. Exp. Biol. 1974, 12, 575-6 (4). Additional references are made in reference (1) to garlic derived preparations having repellent activity towards small animals and also that topical applications of garlic reduced Northern Fowlmite infestations in laying hens. The nematocidal activity of allicin, an extract from garlic, has also been reported in International Journal of Pest Management, 1993, 39(4), 390-392 (5). The molluscicidal properties of garlic have also been reported, D. K. Singh and A. Singh. Allium sativum (garlic), A potent new molluscicide, Biological Agriculture and Horticulture, Vol. 9, No. 2 (6). A review of the antimicrobial properties of allicin are reported by S. Ankri and D. Mirelman in Microbes and Infection, 1999, 125-129 (7).
[0004] An article in the Journal of Medicinal and Aromatic Plant Sciences 2003, 25, PP. 1024-1038, titled “Insecticidal Properties of Garlic”, Singh et al details various conventional methods of preparing garlic extracts such as water extraction, solvent extraction and also details the use of steam distillation to obtain garlic oil.
[0005] An article in the Indian J. Agric. Sciences 1980, 50, PP. 507-510 titled “Extracts of garlic as possible sources of insecticides” details the use of garlic oil obtained by steam distillation from minced garlic cloves; the use of a methanolic extract from garlic; and the use of water and ether extracts obtained when minced garlic was squeezed through a piece of muslin—as insecticides against Spodoptera litura, Euproctis sp. and Culex sp.
[0006] The abstract for an article in the Ind. J. Nematology 1991, 21, pp. 14-18 (Gupta et al) refers to the use of an aqueous extract of garlic which has nematocidal properties. Reference is also made to the use of a distilled oil fraction of garlic which is said to be toxic against nematode lava. Furthermore the abstract details the use of clove powder as a nematocide.
[0007] US Patent Application: U.S. Pat. No. 5,733,552 patent details the use of a dilute garlic juice on grass, shrubs and trees as a means of repelling mosquitoes.
[0008] European Patent Application: EP0945066A1 relates to the use of a mixture of garlic oil or extract which is combined with essential oils to give an improved insecticide/fungicide.
[0009] There are problems associated with the production of garlic oil as it requires a separation of the oil from the natural juice. This normally involves the garlic being crushed and heated to 100° C. in order to carry out a steam distillation. The garlic oil is then separated from an aqueous phase on cooling.
[0010] There are also certain problems inherent with the use of garlic oil, as garlic oil at room temperature is a viscous liquid which is difficult to dilute requiring the use of a carrier solvent which also has to be miscible with the liquid being used as a diluent. The use of such carrier solvents restricts the use of garlic oil in organic farming and introduces other difficulties related to the health and safety aspects associated with the use of such solvents.
[0011] It is therefore advantageous if, rather than isolating the oil from garlic as previously described, the garlic is simply crushed and the juice thus produced used directly. Unfortunately garlic juice isolated in this manner is prone to decomposition through a combination of chemical degradation and microbiological activity. The sulphur components of the garlic juice presumably being oxidized to sulphur dioxide/sulphur and the organic components being oxidized/hydrolyzed to ketones or degraded to carbon dioxide through respiration. As such, if the extracted garlic juice is to be used, it must be freshly isolated from garlic and used almost immediately in order to ensure maximum efficacy as a pesticide/biocide. A markedly decreased level of activity of the material as a repellent may be retained after storage.
[0012] It would therefore be advantageous if a material could be provided which had the properties associated with garlic oil/fresh garlic extract in terms of its repellency to various life forms and its action as a pesticide, but which did not require the steam distillation stage involved in the isolation of the garlic oil. Such a material is described herein together with a process for the production of that material.
BACKGROUND
[0013] The properties of garlic oil and garlic extracts, as described above, are believed to be derived from the presence of allyl polysulphides which are produced following the rupture of the cell walls of garlic during the crushing process. In this process, alliin is converted to allicin by an enzyme called allinase. Subsequently the allicin breaks down to form polysulphides as shown in scheme 1.
[0000]
[0014] It is the allypolysulphides that are believed to give garlic extracts and garlic oil their biological activity and repellency properties. This biological activity of garlic is believed to be due to the allyl polysulphides acting as enzyme inhibitors, metal sequestrants, solvents which are active on cell membranes, respiratory inhibitors and as general antibiotics.
SUMMARY OF THE INVENTION
[0015] In its broadest aspect there is provided a pesticide comprising a liquid concentrate obtained from garlic juice by the removal of water from the juice. The concentrate disclosed herein has the properties associated with garlic oil/fresh garlic extract in terms of its repellency to various life forms and its action as a pesticide, but does not require the distillation stage involved in the isolation of the garlic oil and additionally is stable to long term storage without a decrease in the activity of the material. This stability is due, at least in part, to the removal of water from the extracted juice. This provides a concentrate which possess little or no free water which can be utilized by the living organisms normally responsible for the breakdown of the component parts of garlic juice that give it its biological activity.
[0016] Preferably the water is removed by reduced pressure distillation at a temperatures below 40° C. In this way decomposition of the of the component parts of the garlic extract is minimized during its concentration.
[0017] Preferably the concentrate has a Brix value between 60 and 80. It is the removal of water to give a concentrate with a Brix value in this range that provides the stability observed with respect to the concentrate of the invention disclosed herein.
[0018] Preferably the total poly-sulphides in the concentrate are in the range 2 to 4% w/w.
[0019] Preferably dially sulphides of the formula RSR, RS 2 R, RS 3 R and RS 4 R account for 66%±10% by weight of the total poly-sulphides present (wherein R=allyl group). Preferably the diallyl sulphide: diallyl di-sulphide: diallyl tri-sulphide: diallyl tetra-sulphide are present in the approximate ratio of 4%-5%:5%-8%:31%-38%:19%-22% as weight % of the total poly-sulphides present. A concentrate containing these components, and in these ratios provides a pesticide with a consistent biological activity that might otherwise be obtained due to natural variability of garlic bulbs. Concentrates from a range of feedstock material may be readily blended to achieve this composition.
[0020] Preferably the water is extracted by reverse osmosis.
[0021] In this way a process is provided in which the minimum amount of energy is expended to isolate the concentrate. Additionally the concentrate thus has maximum efficacy as a pesticide as the level of heating to which the concentrate is exposed is minimised.
[0022] Preferably further polysulphides are added to enrich the polysulphide content. Such addition of polysulphides is expected to improve the performance of the mixture as a pesticide, as a repellent and is also expected to improve the residence time of the mixture when applied under open air conditions.
[0023] Preferably the polysulphides are added in the form of garlic oil. Garlic oil is a particularly preferred form of polysulphides to be used for enrichment purposes due to the lack of water in the oil, the addition of materials containing water would destabilize the matrix of the concentrate reducing the stability of the material.
[0024] In a second broad aspect of the invention there is provided a process for the production of a pesticide in the form of a liquid concentrate obtained from garlic by the steps of:
crushing garlic separating the solid material from the liquid produced carrying out a heating stage on the liquid to pasteurize the liquid and removing water from the liquid by reduced pressure distillation at a temperature of approximately 40° C. temperature.
[0029] Isolating and concentrating the garlic juice in this way gives a concentrate which has maximum efficacy as a pesticide and which additionally avoids the expenditure of energy associated with the high temperature distillation normally used to produce garlic oil.
[0030] More preferably the water is removed from the liquid at a temperature of less than 25° C. and at an appropriate reduced pressure. In this way the efficacy of the material produced as a pesticide can be further optimized.
[0031] In a particularly preferred aspect, the water is extracted by reverse osmosis. In this way a process is provided in which the minimum amount of energy is expended to isolate the concentrate. Additionally the concentrate thus has maximum efficacy as a pesticide as the level of heating to which the concentrate is exposed is minimized.
[0032] In a third broad aspect there is provide a pesticidal composition characterized in that it comprises a wood flour based granule impregnated with a liquid garlic concentrate as previously described. A pesticide is therefore provided which is based entirely on materials which occur naturally in garlic and the only residues left by the use of the pesticide are the same residues left by the growing of crops of leeks or garlic. However the use of the pesticide disclosed leaves residues at a much lower level than those observed by the growing of leek and garlic crops. Additionally impregnating a wood flour granule in this way is also believed to result in effectively further drying the concentrate and thus improving the time for which the concentrate maintains its activity. Also improves ease of handling of the material, and its longevity in the field.
[0033] The pesticidal composition in the form of the liquid concentrate or concentrate impregnated granules, as previously described, is particularly useful as an insecticide. It has been shown that the concentrate or impregnated granule disclosed is effective in controlling cabbage root fly and is toxic to mosquito larvae as well as other larvae. It is believed that these results demonstrate that these materials will be effective against a much wider range of insects which are known pests.
[0034] The pesticidal composition in the form of the liquid concentrate or concentrate impregnated granules, as previously described, is particularly useful as a nematocide. The garlic concentrate and impregnated granule disclosed have been found to be particularly effective against nematodes.
[0035] The pesticidal composition in the form of the liquid concentrate or concentrate impregnated granules, as previously described, is particularly useful as an avian repellent. Garlic based products have previously been shown to be effective as repellents to birds. It is therefore reasonable to assume that the liquid concentrate and/or concentrate impregnated granule disclosed herein will also show such activity, but with the additional benefits of the stability conferred by the concentrate matrix.
[0036] The pesticidal composition in the form of the liquid concentrate or concentrate impregnated granules, as previously described, is particularly useful as a rabbit repellent. Results included in the present disclosure show concentrate impregnated granule act as a repellent to rabbits and it therefore reasonable to assume that the concentrate will show the same activity.
[0037] The pesticidal composition in the form of the liquid concentrate or concentrate impregnated granules, as has previously described, may be used as an insect repellent.
[0038] A pesticidal composition characterized in that it comprises a wood flour based granule impregnated with liquid garlic oil. Results disclosed herein show the effectiveness of granules impregnated with the garlic concentrate of the present disclosure and so it is reasonable to assume that garlic oil impregnated onto a wood flour based granule would show similar activity. By impregnating garlic oil onto such a granule the handling of garlic oil would be simplified and the requirement for the use of solvents to used in the dispersion of garlic oil is also removed.
[0039] A pesticidal composition characterized in that it comprises a wood flour based granule impregnated with liquid extracted from freshly crushed garlic. Results disclosed herein show the effectiveness of granules impregnated with the garlic concentrate of the present disclosure and so it is reasonable to assume that liquid extracted from freshly crushed garlic impregnated onto a wood flour based granule would show similar activity. Additionally the extracted juice impregnated onto the wood flour will have improved stability against decomposition as a certain degree of the water will be tied up with the wood flour and further water will be removed by the drying process disclosed herein.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0040] A concentrated garlic juice is produced according to the following method:
1) Fresh garlic is washed; 2) The garlic is crushed; 3) A pressing is carried out to separate solids from liquid; 4) The garlic juice is filtered (the filtration is normally carried out using a 50 micron filter); 5) A pasteurization step is carried out, the juice is heated to a temperature of 90° C. for approximately 30 seconds or a lower temperature of 60° C. for a longer period of up to 2 minutes may be used; 6) A clarification step may then be carried out to remove any suspended material in the liquid; 7) Water is then removed by reduced vacuum distillation.
[0048] This gives the concentrated garlic extract as a viscous brown liquid.
[0049] The water is removed by reduced pressure distillation at a temperature of less than 40° C., as this prevents decomposition of the components of the garlic concentrate and more preferably the pressure is reduced to a point such that the removal of water can be carried out at 25° C.
[0050] It is important to note that none of the prior art cited details the formation of a garlic juice concentrate wherein the water is removed from a garlic juice simply by reduced pressure distillation. All the prior art known to the applicant details the use of standard extraction techniques to isolate the active ingredients from the garlic juice by the use of water extraction, standard solvent extraction techniques or by the use steam distillation to obtain garlic oil.
[0051] Analysis of the concentrate produced by the above method gives analytical data in the following ranges:
[0052] Dry matter (brix); 60-80
[0053] pH (10%. Sol.): 4.0-5.0
[0054] Acidity (meq/kg): 300-400
[0055] (Equivalent to 2.1-2.8% of monohydrated citric acid)
[0056] Available carbohydrates 45-55%
[0057] 1 kg of concentrate is equivalent to approximately 7 kg of fresh garlic
[0058] HPLC Analysis
[0059] The preferred method of analysis for determining the relative ratio of the diallyl polysulphides present in the concentrate is HPLC. Details of the HPLC methods used and the literature method on which they are based are provided in Appendix 1. The third method (RBSULF3) described in Appendix 1 which corresponds to method RBSULF1 with an extended equilibration time is the preferred HPLC method of analysis. A chromatogram obtained from a Garlic Oil Gold standard sample is provided (Chromatogram 1) with the main peaks of the chromatogram identified. Chromatogram 2 is also a chromatogram for a garlic standard. Also shown is a sample chromatogram for a garlic juice concentrate—labelled as—Garlic Product (Chromatogram 3).
[0060] Analysis of the concentrate by HPLC shows the total polysulphides present are in the range of 2.4 to 3.6% w/w. Of these polysulphides, diallyl sulphides of the formula RSR, RS 2 R, RS 3 R and RS 4 R (R=allyl group of the formula —CH 2 CHCH 2 ) are present in the approximate ratio of 4%-5%:5%-8%:31%-38%:19%-22% as weight % of the total poly-sulphides present. These poly-sulphides collectively account for approximately 66%±10% of all the organo-sulphur species present in the concentrate as determined by HPLC
[0061] The concentrate produced by the above process therefore has a high degree of chemical similarity with respect to the polysulphides present in those materials that are found in the liquids produced by simply crushing and processing fresh garlic and to those present in garlic oil.
[0062] The biological activity of the garlic concentrate described herein is believed to be due to this particular ratio of diallyl- and methyl allyl-polysulphides.
[0063] The removal of water in the above manner to provide a garlic concentrate which maintains its stability when stored for prolonged period has clear advantages as compared to the process used to isolate garlic oil, or as compared to the juice obtained by simply crushing fresh garlic. It is believed that the concentrate produced by the above process will maintain activity as described below for at least 3 years, a much longer period that non-concentrated garlic juice. Samples of concentrate were analyzed for a key active component, after storage under typical industry “temperature abuse” conditions, with the following results:
[0000]
Age of
Total Polysulphide
Concentrate
Concentration
3 yr 10 months
2.96 (% w/w)
3 yr 2 months
2.74 (% w/w)
2 yr 9 months
2.67 (% w/w)
1 yr 4 months
3.61 (% w/w)
[0064] The consistency of these analytical results demonstrates the long-term stability of the product.
[0065] Heating of the extracted liquid to a temperature of 60-90° C. for a short period is believed to lead to the conversion of the allicin in the garlic extract being converted to polysulphides with the particular ratio of diallyl polysulphides described herein, this ratio has been found to be particularly effective in the applications described below.
[0066] Preparation of Granules Impregnated with the Garlic Concentrate
[0067] A granular form of the garlic concentrate has also been developed by the inventors. The granules are a formulation of the previously described garlic concentrate impregnated onto woodflour with a binder also present in the ratios shown in table 1 below. Unless otherwise stated, reference to woodflour granules impregnated with garlic concentrate is a reference to granules of the composition shown in table 1.
[0000] Table 1 showing the composition of the granules impregnated with garlic concentrate
[0000]
Chemical
Trade
Content
Chemical Name
CAS. No
Description
Name
Function
(%)
Sodium
9004-32-4
High purity
Blonose
Binder
1.65%
carboxy-
sodium carboxy-
methyl
methyl cellulose
cellulose
(food grade)
Woodflour
Lignin (9005-
Association of
Lignocel
Carrier
53.35%
53-2)
cellulose, lignin
Cellulose
and wood
(9004-34-6)
polyoses
Garlic Oil
800-78-0
Garlic
Active
45%
concentrate (food
ingredient
grade)
[0068] The sodium carboxy-methyl cellulose, woodflour and garlic concentrate are mixed together such that they agglomerate into near spherical pellets/granules between 1 mm and 2 mm in diameter. The granules thus produced are yellowy brown in colour and have a very strong garlic/sulphur odour.
[0069] The granules are subsequently dried by use of warm air at approximately 60° C. for up to 2 hours. Subsequent HPLC analysis of the concentrate contained within the granule shows the same relative amounts of the four allyl sulphides, of the formula; RSR, RS 2 R, RS 3 R and RS 4 R (R=ally group of the formula CH 2 CHCH 2 ), as were found by analysis carried out on the concentrate.
[0070] The efficacy of the granules is very dependant on moisture, see example 5 which relates to the use of such granules to control cabbage root fly (and includes results demonstrating this effect).
[0071] It is believed that forming granules in this way from the concentrate further stabilizes the active components of the concentrate.
[0072] All of the trials described below were carried out in secret and under non-disclosure agreements.
[0073] Rabbit Repellency Trials Using Garlic Granules
[0074] Non-public trials have been carried out which show that granules impregnated with garlic concentrate are effective as a rabbit repellent, see Example 1. These trials provide strong evidence that garlic granules/prills are effective at deterring rabbits from eating carrots when carrots free from garlic are also available, see Example 1. The granules/prills used in the trials were produced from woodflour impregnated with garlic at a level of 5% and/or 20% and, prepared as previously described
[0075] Nematocidal Activity of the Garlic Concentrate
[0076] The garlic concentrate of the present invention has been found to be effective as a nematocide. Initial in-vitro results established the toxicity of the concentrate to nematocides as shown in Example 2 and provided indications of the dilution of the garlic juice concentrate (referred to as NEMguard in Example 2) that should be used in field trials. When the garlic concentrate was used as a liquid formulation through trickle feed irrigation on potato crops, to protect against free living and cyst nematodes, a 14% increase in gross yield of the crop was observed following two applications of the garlic juice concentrate.
[0077] The garlic concentrate referred to as NEMguard has been found to kill almost all nemotocides present within 24 hours at a dilution of 0.05% v/v with water, with 0.1% v/v solution strength total kill can be achieved in 4 hours and with 0.25% v/v solution strength total kill can be achieved in 1 hour. Preferably the NEMguard should be mixed in with water at the end of a plant watering period, in this way elution of the product away from the primary target is reduced. Such treatments should ideally be carried out on a weekly basis during the growing cycle of the crop.
[0078] The critical period during which nematocides should be applied with respect to root crops is the first 4 to 5 week period post drilling. During this time, nematocides attack the delicate new root tip which leads to root forking and strutting with a consequential loss of quality and yield. The impact of free living nematocides can be such that entire crops become un-economic to harvest.
[0079] The LD50 of NEMguard (the garlic concentrate) for free living nematocides has been identified as 0.025% v/v, and has nematocidal effects against both free living and cyst nematocides. The concentrate has been used to protect crops of potatoes, carrots, parsnips, strawberries and melons (n.b. PCN—Potato Cyst Nematode).
[0080] Details relating to the use of granules impregnated with the garlic concentrate referred to as NEMguard are provided in Example 3. The main body of evidence relating to effectiveness of the granules is derived from the use of granules applied through a seed drill with a standard granular applicator as described in Example 3.
[0081] Example 3 also includes reference to in-vitro test results, see 3.2, carried out by dissolving granules impregnated with garlic juice concentrate (referred to as ECOguard granules in section 3.2 of example 3) in water and then introducing specimens of various plant parasitic nematode species into the supernatant. Without exception all species of nematode were killed at solution strengths of 2.5 w/v % granule to water in 2 hours
[0082] The reference in example 3 section 3.3 to NEMguard is a reference to the use of the garlic concentrate and shows efficacy, by the use of in-vitro tests, of the garlic concentrate against the nematode Longidorus elongates as well as other nematodes.
[0083] Example 3 sections 3.4 and 3.4.1 show the effectiveness of woodflour granules impregnated with the garlic concentrate against Globedera pallida (PCN-Potato Cyst Nematode).
[0084] Section 3.5.1, 3.5.2, 3.5.3 of Example 3, Example 3A and Example 3B show the effectiveness of woodflour impregnated granules at reducing the forking observed in carrot crops due to the effectiveness of the woodflour impregnated granules against carrot nematodes.
[0085] Example 4 provides further results relating to the effectiveness of woodflour granules impregnated with the garlic concentrate at reducing root forking in carrots due to the effectiveness of the granules in controlling carrot nematodes.
[0086] Also shown in Example 4 are results relating to the efficacy of a combined application of woodflour granules impregnated with garlic concentrate (NEMguard granules) and garlic concentrate/liquid (CL AIL 0021) for controlling Potato Cyst Nematode (PCN).
[0087] Further results in Example 4 show the effectiveness of woodflour granules impregnated with the garlic concentrate (referred to as ECOguard GR) and of the garlic concentrate (referred to as ECOguard SR and CL AIL 0021) in controlling root-knot nematode Melioidogynae spp., on orient-melon.
[0088] Results are presented in Example 4A showing the effectiveness of garlic impregnated granules (referred to as NEMguard®) at controlling a variety of nematode species i.e. Longidorus elongatus, Pratylenchus crenatus, Tylenchorhynchus dubius and Paratrichodorus pachydermus, in a field used for growing strawberries.
[0089] Cabbage Root Fly
[0090] The use of the granulated form of the concentrate referred to as ECOguard granules has been shown to provide significant reduction in cabbage root fly damage when used on crops of swede, see Example 5.
[0091] Spraying of Cabbage Root Fly eggs directly with a 1% solution of the garlic concentrate showed a lower rate of hatching of the eggs than a control sample of eggs which were not sprayed.
[0092] Poultry Red Mite
[0093] The garlic concentrate has also been found to act as a biocide for reduction of poultry red mite infestations. The concentrate has a particular advantage, as compared to compounds such as cypermethrin (sold under the trade name Barricade), in that it can be applied within buildings infested with red mite with the birds still within the building, but eggs should be removed before use. This is the first botanical biocide, known to the applicants, that has been shown to be effective at reducing poultry red mite infestations, at the recommended use rate the concentrate acts as a contact biocide.
[0094] The concentrate is particularly effective as a biocide when used in confined spaces or in mildly soiled environments.
[0095] Mortality levels in excess of 85% are normally observed in stimulated use studies and similar effects have been reported and observed from confidential field trials: see Example 6.
[0096] The concentrate also functions as a repellent and appears to inhibit recolonisation.
[0097] Conventional biocides tend to have single site action (acetylcholine esterase inhibition) and resistance to these compounds can build up quickly through selection and mutation in the population.
[0098] It is believed that the concentrate disclosed herein (referred to as Breck-a-sol) for use as a control means against Poultry Red Mite) has multi-site action, e.g.
Respiratory enzyme inhibition Membrane disruption and depolarization Metal ion sequestration and chelating in cytosol
[0102] The likelihood of red mites building up resistance to the garlic concentrate is therefore lower due to the biochemical complexity of how the product functions as a biocide.
[0103] Environmental Impact
[0104] The increasing awareness of environmental issues in recent years has lead to the promotion of more environmentally friendly agricultural practices and to an increase in the production of food bearing the organic label. As such the provision of the garlic extract disclosed herein for use as a pesticide or repellent is a significant step forwards, as the decomposition products formed by the use of the extract are entirely natural, corresponding to the same materials left in soil after garlic or leeks have been grown but at a much lower level. Typically commercial crops of garlic and onion will release 120-600 times more polysulphides to soil than a 12 kg/ha application of Ecoguard granules, see reference (1). A detailed analysis of this assertion is provided in Appendix 2 wherein the garlic concentrate is referenced as AIL 0021 and CL AIL.
[0105] Enrichment of Garlic Juice Concentrate by the Addition of Garlic Oil.
[0106] The polysulphide mixture contained in the garlic juice concentrate of the present invention resembles the polysulphide mixture of distilled garlic oil. The polysulphide content of the garlic juice concentrate, produced according to the present invention, can therefore be enriched following its production by the addition of garlic oil. Enrichment of the polysulphide mixture of the garlic juice concentrate in this way gives a material which has an increased level of polysulphides whilst the properties of the garlic juice matrix continue to stabilize the resulting mixture with respect to long term storage. In this way the polysulphide content may be increased to in excess of 7% w/w. The increase in the level of polysulphides in the resulting mixture, is expected to improve the performance of the mixture as a pesticide, as a repellent and is also expected to improve the residence time of the mixture when applied under open air conditions.
[0107] The invention is defined by the claims that follow. It is believed that the pesticide, disclosed herein, is particularly efficacious with respect to its toxicity to mosquito larvae and other insect larvae as well as nematodes, aphids ( Hemiptera ), vine weevils, various beetles ( Coleoptera ), moths and butterflies ( Lepidoptera ), molluscs, mites and cabbage root fly. The material is especially effective as a nematocide.
[0108] In relation to its repellency, the material is particularly effective as a repellent to insects, rabbits and certain avian species.
EXAMPLE 1
Rabbit Feeding Repellency Trials Using Garlic III
[0109] Introduction
[0110] Preliminary non-public experiments on group living rabbits demonstrated a significant effect of garlic as a rabbit feeding repellent. More detailed experiments were conducted on 20 individually housed rabbits. On this occasion, rabbits were selected at random to receive prills impregnated with garlic juice concentrate at levels of 5% or 22%. The prills impregnated with garlic juice concentrate were found to induce a significant repellent effect, although no significant difference in effectiveness was found between the two garlic concentrations.
[0111] Further non-public trials were conducted which were designed to examine the longevity of the garlic repellent response with age of prill. This report provides information on the experimental protocol and summarizes the results of this trial.
[0112] Materials and Methods
[0113] The work was conducted on 20 captive rabbits of wild origin. Although normally penned in pairs, each rabbit was kept individually in three by two metre outdoor pens for five days prior to, and during the experiment. Each rabbit had access, at all times, to commercial pelleted rabbit food, as well as grass growing freely in each pen, and water ad libitum. Rabbits are primarily crepuscular feeders, and so the experiments took place between approximately 15:30 and 09:00 hours. The slightly longer exposure time in comparison to previous trials was unavoidable due to the short day lengths at this time of year.
[0114] Prior to the start of the experiment, prills from a newly opened packet, were pre-weighed when dry, to determine the average number of dry prills needed to stimulate a density of 12 Kg of prills per hectare per bowl. On average, this equated to 5 control prills (containing 0% garlic) and 6 test prills (impregnated with 5% garlic juice concentrate) per bowl.
[0115] Six weeks before the start of the experiment, newly opened packets of control and test prills were then allowed to ‘weather’ in separate pots outdoors. Labelled 23 cm plastic plant pots were filled to approximately 3 cm in depth with gravel, followed by approximately 8 cm of soil (John Innes number 2, soil base compost). The soil was firmed down by watering with approximately 200 ml of distilled water. This was allowed to drain away, and sufficient prills (˜2 g) were scattered on top of the soil to ensure adequate numbers for the duration of the trial. The plant pots were then left outdoors for a period of 2 hours (i.e. fresh prills=0 weeks) or for 2,4,5 or 6 weeks until such time they were used in an experiment. Weathering over the 16 week period included exposure to sun, rain (see below) and temperatures ranging from −12° C. to 20° C.
[0000]
ACTUAL
NUMBER
RAINFALL (mm) > 5 mm THAT FELL IN A
OF DAYS
MONTH
SINGLE DAY
OF RAIN
From 12 th
6.1
14.8
5.7
14.4
13
September
October
16.4
9.5
11.7
15.6
20
November
39.5
12.1
6.7
10.1
23
To 27 th
27.1
7.5
9.0
16
December
[0116] Prior to the start of the trial and during non-experimental days, rabbits were presented regularly with sliced carrot to minimize neophobia. A two-choice test was used, with sliced carrot presented in two separate bowls, one with control prills and one with test prills; 200 g of carrot was presented in each bowl. Bowls were placed in separate feeding stations, located as far apart as possible within the pen to avoid garlic odour impacting upon the control. To avoid position effects, the sitting of feeding stations and bowls was exchanged for the second night of the experiment.
[0117] There were 10 weeks of experiments altogether in this trial, although this did not include the six weeks of weathering of prills prior to the start of the experiment. To avoid habituation effects, each rabbit was tested for the 2 experimental days, once every two weeks. Each of the five ages of prills were tested on all 20 rabbits, i.e. each rabbit was tested five times. Prill ages were allocated to the rabbits using a randomized latin square design. The rabbit feeding experiments began on Oct. 24, 2000 and ended Dec. 28, 2000.
[0118] On the day of the experiment, the requisite number of weathered prills (to stimulate a rate of 12 Kg ha −1 ) was placed onto a damp filter paper (moistened with 3 ml of distilled water) in a glazed earthenware bowl. A plastic coated wire mesh was placed into the bowl, to prevent the prills coming into direct contact with the carrot. This allowed odours from the prills to permeate through the carrot, and mimicked prills lying in close proximity but not in contact with those parts of the vegetation being consumed by rabbits in the field.
[0119] Results
[0120] The percentage of the total food that was eaten over the two days in each feeding station was calculated after subtracting carrot ‘dregs’ that had become inaccessible to the rabbits after falling through the plastic coated grid. An analysis of variance was carried out to investigate the effects of rabbit, week of testing and age of garlic juice concentrate impregnated prills on the total percentage of food eaten (over both feeding stations).
[0121] There was no evidence that the prill age had an effect on the overall quantity of food eaten (p=0.479). However, it was found the quantity of food eaten varied considerably between rabbits (d.f.=16; p<0.001), although there was no evidence that the total quantity of food eaten varied over the weeks (d.f.=16; p=0.104).
[0122] Individual variation between rabbits in the response to garlic juice concentrate impregnated prills is shown in FIG. 1 . FIG. 1 shows a comparison of carrot eaten between feeding stations with prills impregnated with the garlic concentrate and with prills not impregnated with garlic concentrate. It was also noted that only when the prills were fresh was there a more consistent positive feeding response due to the presence of control rather than garlic juice concentrate impregnated prills.
[0123] For analysis of the effect of garlic, the percentage of carrot eaten at the station with garlic prills was subtracted from the percentage at the control station, to give the reduction in the percentage of carrot eaten due to garlic juice concentrate. The mean reduction in percentage of carrot eaten at the different ages of prill is given in the table below.
[0000]
Prill age (weeks)
0
2
4
5
6
Mean reduction in
22.6%
4.9%
0.7%
3.6%
1.5%
percentage of carrot
eaten from garlic versus
control bowl
[0124] ANOVA indicated that there was strong evidence (p=0.007) that on average, the rabbits ate less carrot from the feeding station with garlic prills, on average when the prills were fresh, than when the prills were older. There was no evidence (p=0.5) that prills weathered two weeks or more were effective. At the 95% confidence interval, the reduction in carrot eaten when fresh prills were used, ranged from 10% to 36%.
[0125] Note that no evidence was found for a carry-over effect from the age of prill experienced by a rabbit on the previous occasion of testing.
[0126] Thus, it appears that the fresh prills did have an effect on the preference of the rabbits, although there was no evidence that prills weathered for two weeks or more were effective.
[0127] Conclusions & Recommendations
[0128] There is strong evidence to suggest that garlic is effective, when presented as fresh prills, at deterring the majority of rabbits from eating carrot when carrot free from garlic odour is also available. However, there is no evidence that this response will continue once the prills have been weathered during the autumn and winter, for two or more weeks.
[0129] Based on the consistent and outstanding results with fresh prills, it is recommended that a similar experimental trial is conducted, but at a higher percent garlic dose per prill, which may counter the apparent deterioration by weathering, and thus extend the longevity of this response. Specifically, the percentage of garlic juice concentrate in the prills could be increased to 11% or 22%. Increasing the prill density from 12 Kg ha −1 to 20 Kg ha −1 or higher (maximum density of 150 Kg ha −1 ) may not achieve the increased longevity if the prills are equally exposed to the weather?
EXAMPLE 2
Use of Garlic Juice Concentrate (NEMguard®) Against PCN (Potato Cyst Nematode- Globodera Pallida )
[0130] NEMguard® is a garlic juice concentrate which acts as a powerful nematicide.
[0131] A sequence of developmental work with NEMguard® formulations has identified clear evidence of nematicidal effects against both free living and cyst nematodes.
[0132] The liquid formulation of NEMguard® in particular lends itself to delivery through trickle feed irrigation and preliminary work conducted on potato crops produced very encouraging results, with a 14% increase in gross yield attributed to two applications of NEMguard®. This non-public trial was in a field with a significant Potato Cyst Nematode (PCN) population.
[0133] In-vitro work has enabled the inventors to further develop the field protocol. The protocol on product use rate is presented below.
[0134] 1.0 Strength of Use of Solutions
[0135] It has been shown that solutions of the garlic juice concentrate (NEMguard®) as dilute as 0.05% v/v produce almost total kill within 24 hrs. With 0.1% v/v solution strengths total kill can be achieved in 4 hrs. With 0.25% v/v solution strength, total kill can be achieved in 1 hr. Use of the concentrate should therefore be planned to operate within these three dilutions as a balance between efficacy and cost.
[0136] Option 1 (Timed)
[0137] If it is assumed that the concentrate is added to a 1000 litre volume at the end of an irrigation sequence, then the following ratios of volume addition are needed.
[0000]
@ 0.05% v/v in 1000 litres =
0.5 litre NEMguard ®
@ 0.1% v/v in 1000 litres =
1.0 litre NEMguard ®
@ 0.25% v/v in 1000 litres =
2.5 litre NEMguard ®
[0138] Ideally the percolation time for the last 1000 litres should be managed to maximize persistence in the soil volume expected to contain migrating PCN. Clearly addition at the end of the sequence reduces elution of the product away from the primary target. It is assumed that soil at or close to field capacity, will show reduced drainage, thereby enabling the delivery dose to be maintained for as long as possible.
[0139] It is preferable to mix the NEMguard® with the last 1000 litres of water prior to pumping out. If this is not possible, then the NEMguard® should be added to the pipe work over a period of several minutes to increase the chances of adequate mixing.
[0140] Option 2 (General)
[0141] If we assume that the garlic juice concentrate (NEMguard®) is to be added over the entire irrigation delivery event ˜9000 litres over 1-2 hrs, the following volume additions need to be considered:-
[0000]
@ 0.05% v/v in 9000 L =
4.5 litres
@ 0.1% v/v in 9000 L =
9.0 litres
@ 0.25% v/v in 9000 L =
22.5 litres
[0142] Consideration of the two delivery approaches, timed and general identifies single event use rate volumes of between 2.5 1 and 22.5 1 as likely to give evidence of efficacy.
[0143] In view of the rapidity with which NEMguard® kills nematodes the overall approach should be maximization of peak dose, whilst minimizing water volume on the grounds of economics.
[0144] The permutations increase considerably if the total rate/ha is increased thereby making more product available.
[0145] 2.0 In Conclusion
[0146] The LD 50 of NEMguard® for free living nematodes has been independently determined at ˜0.025% v/v. This clearly gives considerable scope for product delivery strengths substantially above this value whilst still being economic relative to other nematicides.
[0147] The rapidity with which NEMguard® kills favours “bursts” of relatively high solution strength that could be managed to persist by being added at the back end of an irrigation event.
[0148] This approach also allows several repeat applications at for example weekly intervals for six weeks.
[0149] The alternative is to apply the product as a single high dose through an entire irrigation event.
[0150] If management and infrastructure of the system allow, multi burst approach should be considered.
[0151] 3.0 Schematic Protocol
[0152] Assume 9000 1 delivered in 1-2 hrs. 1000 litres take 6.6 minutes to pump (1 hr rate)
1 Pump 7000-8000 litres of normal water in to crop. 2 Add 2.5-5 L NEMguard® to last 1000 litres, this is ˜53 mins (6.6 mins left) 3 Pump out 4 If addition of NEMguard® tales 2 mins, then last pulse is diluted in ˜660 litres which should be adequate to distribute the product. 5 Repeat weekly for either 3-6 weeks depending on solution strength used and total rate/Ha selected.
EXAMPLE 3
Effectiveness of the Garlic Concentrate and Granules Impregnated with the Concentrate Against Nematodes
[0158] 3.0 Summary
[0159] A programme of non-public field trials in potato and root vegetable crops has identified commercially significant levels of damage reduction where the proposed formulations formulations (NEMguard®) have been applied to control nematodes.
[0160] The main body of evidence is derived from the use of granular products applied at drilling, when compared to the efficacy of products such as Temik. A limited number of trials have been carried out by independent organizations approved by the Pesticide Safety Directive, or similar organizations accredited in their own country (South Korea). Conclusions in these reports support the claim that NEMguard(® has nematacidal properties.
[0161] The most advanced formulation, in granular “NEMguard” form, appear well suited as an alternative to Temik and Vydate in root vegetables.
[0162] There is a high degree of consistency within the in-vitro and field experimentation.
[0163] 3.1 Preliminaries
[0164] In the time that the inventors have been examining garlic products for use in crop protection, the potential for a formulation as a nematicide has become increasingly clear. A combination of in-vitro primary screening and replicated non-public field trials in potato, parsnip, carrot and melon crops in Europe and Korea has provided evidence that nematodes can be killed by the chemicals in the garlic products (NEMguard®). Plants in the field appear to respond to sub-surface applications of the granules and liquids with significant increases in vigour and gross yield, which appear to relate to nematicidal effects.
[0165] In the case of root vegetables such as carrot there is clear independent evidence that quality issues such as root forking and stunting caused by free-living nematodes can be significantly reduced from a single application of NEMguard® granules applied at drilling.
[0166] Controlled experiments in vitro and controlled bioassays in vivo with Longidorus elongates and Globodera rhostochiensis also provide evidence that NEMguard® is a powerful nematicide with efficacy comparable to that seen with Temik.
[0167] The European review of pesticide active ingredient is expected to lead to the removal of approximately 66% of the presently approved active substances by around 2007. Nematicide products such as Aldicarb are already under intense scrutiny. Derogation has been granted for its use in approved crops up until 2007.
[0168] There is therefore a huge opportunity for environmentally benign products that have nematicidal/nematistatic activity to replace those highly toxic products such as aldicarb, vydate and methyl bromide
[0169] 3.2 Introduction to the Program
[0170] The preliminary bio-assay work with garlic against nematodes was carried out in 1998. This work involved dissolving prototype ECOguard granules formulated with garlic juice concentrate in water and then introducing specimens of various plant parasitic nematode species into the supernatant. Without exception all species were killed at solution strengths of 2.5% w/v granule to water in 2 hrs.
[0171] In the case of Globodera pallida (PCN) and Longidorus elongates (root fanging), mortality reached these levels in four hours with solution strengths of 1.25% w/v. In the case of Longidorus spp. significant mortality occurred at 24 hrs with solution strength's of 0.25% w/v.
[0172] Since these primary screening experiments, the inventors have maintained a research and development programme on nematology, through a combination of non-public field trials and further in-vitro research.
[0173] The data from both in-vitro and field scale usage of the formulations has clearly identified nematicidal properties at use rates that are economic. This is particularly the case where granules have been applied to crops of root vegetables such as carrots and parsnips to protect them from free-living and cyst nematode damage.
[0174] 3.3 Results
[0000]
TABLE 3.3.1
Effects in vitro, percentage mortality (SCRI 1998). First experiments
with garlic juice concentrate (NEMguard ®)
Nem species/
2 hrs
4 hrs
6 hrs
24 hrs
Rate of product
Contact
Contact
Contact
Contact
Paratrichodorus
2.5%
100
100
100
100
1.25%
0
100
100
100
0.25%
0
4
14
Control prill
0
0
0
0
Golbodera
2.5%
100
100
100
100
1.25
98
100
100
100
0.25%
7
13
18
72
Control prill
0
0
0
0
Longidorus
2.5
100
100
100
100
1.25
77
100
100
100
0.25
3
4
34
58
Control prill
0
0
0
0
[0175] The data above clearly shows that there is a toxic material to nematodes in the “NEMguard®” formulation.
[0176] This result was confirmed, when garlic juice concentrate was used in an in-vitro bioassay comparing rate of kill against solution strength. FIG. 2 is a graphical representation showing the; in-vitro bioassay of the garlic juice concentrate against Longidorus elongatus. Mortality is grouped according to contact time (1-24 hrs) at the various dilutions.
[0177] The data indicates that the LD 50 at 24 hrs is 0.025%.
[0178] 3.4 Impact of the Granules on Free-Living Nematodes
[0179] The non-public field trials in potato crops provided evidence of an impact on PCN as rate of application increased. When NEMguard® was applied to crops of root vegetables, the impact of the product can be assessed through differences in the amount and type of root malformations attributed to nematode feeding.
[0180] The UK root vegetable industry relies very heavily on Temik as a means of reducing root damage and promoting yield in crops of carrot and parsnip. In 2003, the inventors initiated a program of non-public field trials to evaluate the potential for NEMguard® to replace Temik in these vegetable crops.
[0181] When root vegetable crops are established, Temik is co-applied with the seed into the same furrow and offers protection to the emerging radicle. Nematodes attack the delicate new root tip, which leads to root forking and stunting, with a consequential loss of quality and yield. The impact of free-living nematodes can be such that entire crops become un-economic to harvest.
[0182] 3.4.1 Parsnip Crop—at Hainford (Norwich)
[0183] In non-public trials at Hainford (Norwich), the inventors laid out an 8 replicate, 6 treatment randomized block, with Temik included at a rate that reflected commercial best practice. NEMguard® was included at four rates: 5,10,15 and 20 kg/ha and all these were referenced against an untreated control. All applications were made through a commercial seed drill with standard granular applicator. The site had been tested for nematode populations and was considered to be at risk of damage, with Temik applications justified.
[0184] The crop was assessed at an intermediate stage in maturity and the proportion of forked and fanged roots determined.
[0185] A significant difference in root fanging occurred within the treatments, this is illustrated in FIG. 3 , which shows root forking in parsnip crop at Hainford (Norwich).
[0186] The boxes ( FIG. 3 ) represent the inter-quartile ranges, which contains 50% of values. The whiskers are lines that extend from the box to the highest and lowest values across the replicates, excluding outliers. A line across the box indicates the median. Treatments are significantly different.
[0187] Treatment
[0000]
1 =
Control
2 =
Temik (aldicarb)
3 =
NEMguard ® 5 kg/ha
4 =
NEMguard ® 10 kg/ha
5 =
NEMguard ® 15 kg/ha
6 =
NEMguard ® 20 kg/ha
[0188] The control (treatment 1) had significantly more forked and fanged roots than all the NEMguard® treatments (3-6), 5-20 kg/ha respectively. The NEMguard® treatments at 10-20 kg/ha were significantly better than Temik. At this trial site there was also evidence of increased plant stand with increasing NEMguard® applications ( FIG. 4 )
[0189] FIG. 4 —Plant Stand in Relation to Treatment.
[0190] The bars represent the range of values from individual replicates. The Temik and all NEMguard® applications appear to increase plant stand over the control. The 20 kg/ha rate of NEMguard® almost separates from the control.
[0191] Taken together, the data on root forking and plant stand numbers are good evidence that NEMguard® was as effective as Temik in defending the crop from plant loss and root damage.
[0192] 3.5.1 Carrot Trial Posketts Farm, Yorkshire
[0193] A complimentary trial to that on the parsnips was run on carrots. This non-public trial compared the effect of 20 kg/ha rates of NEMguard® against Temik applied at a rate reflecting commercial best practice. All treatments were referenced against an untreated control. The site was selected on the basis of nematode numbers determined from soil sampling.
[0194] The trial was laid out in three replicates with all treatments applied through a conventional tractor mounted drill.
[0195] Table 3.5.1 Impact of NEMguard® on Root Forking and Stunting. Summary of Trial Results at Posketts Farm, Yorkshire
[0196] 4 Replicate, randomized block
[0000]
TABLE 3.5.1
Impact of NEMguard ® on root forking and stunting. Summary of trial
results at Posketts Farm, Yorkshire
4
Replicate, randomised block
1
Control
2
Temik
3
Standard ECOguard ® 20 kg/ha
Control
Temik
EG (standard)
Percent of fanged and stunted roots in each replicate.
Block 1
3.2
3.0
4.8
Block 2
11.1
4.4
2.8
Block 3
16.8
7.7
7.8
Block 4
8.6
9.0
4.5
Mean/rep
9.92
6.02
4.97
Total number of roots sampled/treatment
441
505
421
[0197] A statistical analysis of the data did not reveal significant differences between treatments. The data does have some clear trends, with the control having ˜50% more fanged and stunted carrots than the other treatments. The large number of roots examined/treatment adds further confidence to the robustness of the effects.
[0198] Drawings illustrating the symptoms seen across one of the blocks are given in FIG. 5 .
[0199] The trial provided good evidence that NEMguard® formulations significantly reduced root forking and stunting to at least the extent noted with Temik in the same trial.
[0200] 3.5.2 Further Trial Results Relating to Prevention of Root Fanging in Carrots Caused by Nematodes.
[0201] In response to pressure to find alternatives to Temik, a group of non-public trials was run to compare and contrast the efficacies of Temik, Vydate, Nemathorin and Nemguard. The trials on carrots were spread over three sites in Norfolk, Yorkshire and Nottinghamshire and included NEMguard® at 20 kg/ha applied at drilling. A summary table of the percentage of root forking at each site is given below in table 3.5.1
[0202] All sites had been specially selected on the basis of populations of free-living nematodes in soil samples.
[0000]
TABLE 3.5.2
Relative differences in percentage of root forking in 3 carrot crops.
Means
Trial 1,
Trial 2,
across all
Product
Rate/ha
Notts
Norfolk
Trial 3, Yorks
trials
Untreated
14.3
17.2
14.1
15.2
Temik
8.45
6.3
6.0*
13.7
8.6
Vydate
13.75
9.3
10.4
11.0
10.2
Vydate
20.0
9.2
8.4
15.2
10.9
Vydate
25.0
7.5
6.6*
14.9
9.6
Vydate
55.0
9.0
9.4
9.1
9.2
Nemathorin
17.8
14.3
8.7
10.6
12.2
NEMguard ®
20.0
11.2
4.7*
12.8
9.6
*Significantly better then control
[0203] Significant treatment effects occurred at the Norfolk site, where NEMguard® was the most effective treatment, reducing root forking by 73%. In contrast, Temik reduced root forking by 65%. Collectively across all the three trial sites, NEMguard®, Temik and Vydate (at all rates) exerted very similar levels of control.
[0204] 3.5.3 Trials with NEMguard® Against Carrot Cyst Nematode
[0205] The inventors conducted a group of non-public pot experiments with carrots planted in field soil with a history of producing crops affected by yield and quality loss attributed to the activities of carrot cyst nematodes Heterodera carotae.
[0206] When these experiments were assessed, there was evidence of a treatment and dose affect on symptoms caused by carrot cyst nemtodes. NEMguard® applications at a rate equivalent to 30 kg/ha appeared superior to any other treatment.
[0207] A non-public field scale study was initiated following the pot experiment, where four rates of NEMguard®, 10, 20, 30 and 40 kg/ha were compared to an untreated control. This trial was assessed independently and produced a clear treatment and dose effect of economic importance. All NEMguard® applications increased saleable yield in the trial. The greatest gain occurred with NEMguard® applied at 20 kg/ha, which increased total yield by 12.6 tons/ha.
[0208] The effects of NEMguard® in the field trial are shown in table below. The number of saleable roots also increased with 10-30 kg/ha ECOguard®.
[0209] With the following assumptions use of ECOguard® in carrots offers substantial economic gain:
[0210] The average harvest in the autumn is 100 tons/ha.
[0211] The average sale price pr kg is 0.78 Dkr.
[0212] Approximately 1.000.000 carrots pr hectare with an optimal weight of 100-gram pr carrot.
[0000]
TABLE A
The economic benefit of using ECOguard ® in Lammefjorden carrots.
Total
Saleable
Extra
Total
Extra
extra
carrots
yield
weight
yield
yield
Treatment
(tons/ha)
(tons/ha)
(tons/ha)
(tons/ha)
(tons/ha)
0 kg
69.4
—
75.0
10 kg
73.4
4.0
76.6
1.6
5.6
20 kg
76.2
6.8
87.6
12.6
19.4
30 kg
78.5
9.1
86.3
11.3
20.4
40 kg
73.1
3.7
79.8
4.8
8.5
[0213] The data in table A, above, clearly identifies a dose response, with optimal effects seen at 20 kg/ha of NEMguard®.
EXAMPLE 3A
[0214] Non-Public Trial with Carrot Cyst Nematode
Purpose: The purpose of the trial was to observe a possible dose-response on the attack of the carrot cyst nematodes, in order to determine the optimal dose to be used in a field trial.
[0216] Crop: Carrots F 1 CR 501. Coated with Thiram.
[0217] Trial start: 15 Jan. 2004
[0218] Trial assessment: 7 of April 2004 & 11 May 2004.
[0219] Plots: 10 rows of pots per treatment. No replications.
[0220] Plants: 10 seeds per pot
[0221] Treatments: Untreated
10 kg/ha=14 granules/pot=50 mg/pot 20 kg/ha=28 granules/pot=100 mg/pot 40 kg/ha=56 granules/pot=200 mg/pot 80 kg/ha=112 granules/pot=400 mg/pot
Seeds and granules were covered with approx. 0.5-1 cm soil in the pots.
[0227] Results:
[0228] At the first assessment in the beginning of April there was a big difference in the appearance of the roots between the different treatments. The untreated carrots had less white roots than the carrots treated with 10-80 kg/ha. There was no visible difference on doses. The carrots were very small and it was decided to wait another month before the final assessment.
[0229] It was not possible to make a statistical analysis in this screening trial because there were only 10 pots per treatment. The results can therefore only show a tendency of what can be expected in the field.
[0000]
TABLE 1
The results divided among treatments.
Treatments (kg/ha)
0
10
20
40
80
Average Number of cyst
14.4
12.7
9.1
6.6
8.3
Average length of the longest leaf
11.28
11.00
12.67
12.78
11.83
Average Vigour score
2.33
2.11
2.89
3.33
3.11
[0230] Vigour Score:
[0231] 1: Poor
[0232] 2:
[0233] 3:
[0234] 4: The best plants
[0235] Number of Cyst:
[0236] The number of cysts was roughly counted per carrot. An average of the number of cysts for all the plants per pot was estimated.
[0237] The number of cysts seemed to decrease with increased doses of garlic concentrate. The length of the longest leaf and the vigour of the plants tended to increase with increasing the dose. The dose of 80 kg/ha may be phytotoxic because the length of the leaves and the vigour score decreased compared to the previous doses but at the same time it seemed the number of cysts increased.
[0000]
TABLE 2
The average number of cyst and the length of the longest root divided
among categories.
Category of vigour
1
2
3
4
Average number of cyst
16.00
10.7
8.8
9.1
Average length of the longest leaf
10.8
11.2
11.8
13.08
[0238] It can be seen from table 2, that the number of cysts decreased markedly from the poorest category 1 to the best category 4. The average length of the longest leaf increased though the categories.
[0239] The figures in table 2 confirmed the visible difference observed between the plants.
[0000]
TABLE 3
Percent of pots in each category of vigour (9 pots pr treatments)
Treatments (kg/ha)
0
10
20
40
80
Category 1
22%
11.1%
11%
0%
11%
Category 2
30.3%
66%
11%
22%
11%
Category 3
31.3%
22%
55.5%
22%
33.3%
Category 4
11%
0%
22%
55.5%
44.4%
[0240] It can be seen from table 3, that the majority of good vital plants moved from category 2 to category 4 with the increased dose from 10 to 40 kg/ha. With 10 kg/ha there were no plants in category 4. With 40 kg/ha there were no plants in category 1 but more than half the plants were in category 4. Thus, there was a tendency for more vigorous plants with increasing dose of ECOguard. It can be seen that 80 kg/ha wasn't as good as 40 kg/ha.
[0241] Conclusion:
A dose-response was observed. The number for carrot cyst nematodes decreased with the application of 10-40 kg/ha. The vigour and the length of the longest leaf increased with the application of 10-40 kg/ha. The highest number of pots in high categories for vigour (3-4) was found with the application of 20-40 kg/ha. The optimal dose for carrot cyst nematodes is probably 20-40 kg/ha.
EXAMPLE 3B
Further Results Showing the Efficacy of Garlic Concentrate Impregnated Granules Against Cyst Nematodes in Carrots
[0247] Background:
[0248] In Lammefjorden on Sealand, carrots have been grown for many years because the soil is rich in nutrients and have an ideal structure for carrots. Unfortunately the many years on the trial site of carrot production have increased the pest pressure of cyst nematodes to such a degree that carrot production on many soils is impossible.
[0249] Purpose:
[0250] The purpose with of the trial was to investigate if the attack from cystenematodes in late carrots could be decreased /reduced.
[0251] Trial Plan:
[0252] In non-public trials, one hectare of infected nematode soil was divided into 6 rows and drilled with carrots seeds and ECOguard Granules. There were two untreated rows. 6 plots per row with carrots were dogged up and measured (approx 80-100 carrots pr plot).
[0000]
Treatments:
0 kg/ha
10 kg/ha
20 kg/ha
30 kg/ha
40
0
kg/ha
kg/ha
[0253] The carrots were drilled and treated on the May 12, 2004.
[0254] The trial was assessed on the Sep. 25, 2004.
[0255] A band of one meter with four rows was dogged up, sorted, counted and weighed. A growth difference could be seen between untreated and 20-30 kg ECOguard/ha.
[0256] Results:
[0000]
TABLE 2
The number of good and bad carrots.
No. of good
% Increase in
No. of bad
Total no. of
Number
carrots
good carrots
carrots
carrots
0 kg
48.67
37.83
86.50
10 kg
59.33
+15.7
38.33
97.67
20 kg
48.17
−1.0
27.00
75.17
30 kg
58.00
+19.2
26.00
84.00
40 kg
51.17
+5.1
34.33
85.50
[0257] The number of good carrots increased with an application of 10 to 30 kg/ha ECOguard. The treatment with 20 kg/ha had approximately the same number of carrots in the rows as the untreated carrots. There is no explanation for the diminished number of carrots.
[0258] 10 and 30 kg/ha ECOguard gave 16-20% more saleable carrots. The number of bad carrots decreased. The total number of carrots increased on average by 11 carrots per one-meter row.
[0259] There is a tendency that the carrots respond with phytotox to the application of 40 kg/ha ECOguard. It can be seen in the table above and in the tables below that 40 kg/ha doesn't improve the quality of the carrot.
[0260] FIG. 4 shows the types of deformation caused by cyst nematodes i.e. small carrots with compressed tips, split and deformed carrots
[0000]
TABLE 1
The weight of good and bad carrots.
Weight of good
Weight of bad
Total weight
% Weight
Treatment
carrots (g)
carrots (g)
(g)
increase
0 kg
4494.08
1964.17
6458.25
—
10 kg
5391.00
1950.83
7341.83
+13.7
20 kg
4922.33
1545.50
6467.83
+0.15
30 kg
5583.33
1529.83
7113.17
+10.1
40 kg
4921.17
1820.17
6741.33
+4.4
[0261] The weight of the good carrots increased from 10 to 30 kg/ha. The total weight increase was 10-13.5%. Again 20 kg/ha doesn't fit into the trend.
[0000]
TABLE 2
The average number of roots per plot, average root weight, percentage
increase in average root weight and percentage saleable carrots.
Average
Average
% Increase in
number of roots
root
average root
% Saleable
Treatment
pr plot
weight (g)
weight
carrots
0 kg
86
75.0
69.4
10 kg
94
76.6
+2.1
73.4
20 kg
76
87.6
+16.7
76.2
30 kg
84
86.3
+15.0
78.5
40 kg
89
79.8
+6.5
73.1
[0262] It can be seen that the average number of roots pr plot was highest for 10 kg/ha. The lowest number of carrots was with 20 kg/ha. Perhaps the drill didn't drill the seeds properly. There was no significant difference between 0, 10, 20, 30 & 40 kg/ha.
[0263] The average root weight increased with 10-30 kg/ha. The increase was between 15-17% root weight.
[0264] The number of saleable roots increased with 10-30 kg/ha ECOguard.
[0000]
TABLE 3
The economic benefit of using ECOguard in Lammefjorden carrots.
Total
Saleable
Extra
Total
Extra
extra
carrots
yield
weight
yield
yield
Gross margin
Treatment
(tons/ha)
(tons/ha)
(tons/ha)
(tons/ha)
(tons/ha)
Dkr/ha
0 kg
69.4
—
75.0
10 kg
73.4
4.0
76.6
1.6
5.6
4.370.00
20 kg
76.2
6.8
87.6
12.6
19.4
15.130.00
30 kg
78.5
9.1
86.3
11.3
20.4
15.910.00
40 kg
73.1
3.7
79.8
4.8
8.5
6.630.00
[0265] The average harvest in the autumn is 100 tons/ha.
[0266] The average sale price pr kg is 0.78 Dkr.
[0267] Approximately 1.000.000 carrots pr hectare with an optimal weight of 100-gram pr carrot.
[0268] Conclusion:
[0269] There was a clear tendency for reduction of cyst nematode attack in carrots.
[0270] The number of saleable carrots increased with 17% with 30 kg ECOguard/ha and the average root weight increased from 75 gram to 86 gram. An optimal carrot weights 100 gram.
[0271] The carrots were only treated once at drilling—the optimal doses are 2-3 treatments during the growing season with either granule or liquid form garlic concentrate. For example granules at drilling and liquid during the growing season.
EXAMPLE 4
[0272] 7.3 ECOguard as a Nematicide
[0273] 7.3.1 Carrot Trial
[0274] Data from the non-public carrot trial at Posketts (see example 3) has been analyzed and shows a clear trend towards reduction in root forking where NEMguard granules had been applied at time of drilling. The magnitudes of effects are illustrated graphically in FIG. 6 , where the treatment against the rate of forking is shown.
[0275] Treatment 1 is the control, treatment 2 is Temik and treatments 3&4 are 20 kg/Ha application of NEMguard granules. The 2 NEMguard applications are almost statistically separate from the control and very similar to the pattern of data seen at Hainford with respect to parsnips (see example 3). At the very least, NEMguard and Temik appear to produce similar levels of effect within the two crops.
[0276] 7.3.2 PCN at Needham Field, Yaxley
[0277] Following a report on apparent gross yield increase where NEMguard granules and CL AIL 0021 liquid (garlic concentrate) were used in combination, the field was re-sampled in order to determine the residual PCN egg/gram at the end of the crop production cycle. These results have been compared to the initial egg/gram data and are presented below in table 7.3.2.
[0000]
TABLE 7.3.2
PCN numbers at Needham Field, Yaxley
Sector/treatments
Initial egg/gram
Final eggs/gram
Fp/Ip ratio
1 granules + liquid
(15)
0
0
2 granules only 30 kg
16
5
0.3
3 granules only 30 kg
18
1
0.05
4 granules + liquid
35
46
1.31
[0278] The data in table 7.3.2 above does suggest a high degree of inhibition of PCN reproduction.
[0279] The most important data observed is in sector 4 where there was a commercially very significant population of PCN found at the start of cropping. The re-sample data also confirms the presence of a high PCN population in this sector, but the rate of increase in the population due to the potato crop appears to have been minimal and is essentially the same as that found at the start. This is a very significant result as use of nematicides in potato crops is primarily to inhibit PCN reproduction and ideally keep the population of egg/ gram as close to that at the commencement of the crop.
[0280] An Fp/Ip ratio of 1.31 would normally be acceptable to the Pesticides Safety Directorate (PSD) as proof of nematicidal effects.
[0281] 7.3.3 Root Knot Nematode Control in Sun Melons (Korea)
[0282] In non-public trials, the efficacy of NEMguard (granules impregnated with the garlic concentrate) and CL AIL 0021 liquid (the garlic concentrate) as nematicide to root knot nematodes has been evaluated.
[0283] The resulting report states that significant differences with treatments vs. the control were found, with all ECOguard formulations being statistically equivalent to Carbofuran.
[0284] In conclusion, the report states “Compared to Carbofuran Eco-guard GR and SR showed 83.5-94.9% control efficacy 30 days after treatment and 87.9-97.1% control efficacy (after 60 days) without phytotoxicity. Therefore the products can be used as a nematicide to root-knot nematode Meloidogynae spp., on orient-melon”
[0285] A re-evaluation of the data suggests that due to irregular distribution of initial nematode numbers in the treatment replicates at the start, the degree of efficacy compared to carbofuran may be less than that quoted above, but nonetheless is substantial, with the 1.25% solution strength having 77% of the efficacy of Carbofuran.
[0286] Even allowing for a degree of caution in interpreting the results, the Korean data is good evidence of CL AIL 0021 formulations acting as a nematicide to a genus of widespread distribution and major economic importance.
EXAMPLE 4A
Efficacy of NEMguard® Against Soil Living Nematodes in a Field Used for the Growing of Strawberries
[0287] In non-public field trials, the following results demonstrate the efficacy of the garlic concentrate in controlling nematodes in a field infested with a number of different species of nematodes, said field being used for growing strawberries. If such infestations are not controlled it can result in such crops of strawberries having to be abandoned.
[0288] In Norway, the needle nematode Longidorus elongatus is a serious root parasite of strawberry, with a damaging threshold of 3-5-ind./250 g soil. Good fields have been abandoned due to L. elongatus, and in severe cases 2 crop years have been lost.
[0289] Effects of NEMguard® treatments on the growth parameters in 1 st year strawberry (cv. Polka) were studied in a field infested with Longidorus elongatus, Pratylenchus crenatus, Tylenchorhynchus dubius and Paratrichodorus pachydermus at Marnardal, southern Norway 2005. Significant difference (S) to strawberry control noted at P≦0.05, and a tendency (t) was registered in the range 0.10≧P>0.05; Non-significant difference (NS) noted for P>0.10; 2-sample test.
[0000]
NUMBER
NUMBER
NUMBER
GROWTH
OF
OF
OF
TREATMENT
RATING
LEAVES
RUNNERS
CROWNS
NEMguard ® 8 g/m2
S
S
t
NS
NEMguard ® 16 g/m2
S
NS
NS
NS
NEMguard ® 32 g/m2
S
S
NS
NS
NEMguard ® is a reference to granules impregnated with the garlic juice concentrate.
EXAMPLE 5
An Overview of the Efficacy Data from Field Trials with ECOguard Granules Used to Control Cabbage Root Fly Damage in Norway
[0290] 1.0 Preliminaries
[0291] An extensive program of non-public field trials, which included five crops of swede were carried out. The field trials design was based around multiple applications of either ECOguard® liquid (garlic juice concentrate) or granules (wood flour granules impregnated with the garlic juice concentrate) and in four out of the five swede trials was referenced against Dimethoate as a standard.
[0292] Analysis of the raw data from all the swede trials conducted by the inventors revealed significant treatment differences in cabbage root fly damage in two from five trials (Romedal and Toten). At Toten, the reduction in cabbage root fly damage led to a 28% increase in saleable yield.
[0293] Overall, Dimethoate and ECOguard® appeared to reduce cabbage root fly damage by similar levels although this was only significant at Toten.
[0294] A comparison of two trials (Toten and Ga-Fa), with similar levels of cabbage root fly damage (RDI in controls 57.33 and 68.69 respectively) but widely differing patterns of rainfall during treatment applications, clearly revealed the impact of rainfall of efficacy. Episodes of heavy and persistent rain appeared to remove any efficacious effects.
[0295] 2.0 Results
[0296] The overall effects are summarized in tables below.
[0000]
TABLE 1
Combined root damage index (RDI) four new sites
Sor
%
Treatment
Mid-Troms
Ost
Ga-Fa
Toten*
Mean
Change
Control
38.29
24.33
68.69
54.67
46.49
—
Dimethoate
40.60
24.92
65.78
44.33
43.90
−5.8
ECOguard ®
36.29
24.33
71.67
42.24
43.63
−6.5
*Significant difference from control and 3 applications of ECOguard ® granules.
[0000]
TABLE 2
mean saleable yields at each site, kg/sample (cat 1 + 2, Norwegian
notation, 1 = undamaged, 2 = slight damage)
Mid-
Treatment
Troms
Sor Ost
Ga-Fa
Toten
Mean
% Change
Control
5.29
19.87
7.78
11.05
10.99
—
Dimethoate
5.84
22.16
7.27
11.95
11.95
+8
ECOguard ®
5.81
23.62
6.81
15.35
12.89
+15
[0297] The data in table 1 and 2 above indicate a mean reduction in cabbage root fly damage associated with both Dimethoate and ECOguard®. At Toten reductions in cabbage root fly damage were significant.
[0298] ECOguard® produced the greatest gain in saleable material across the four sites, approximately doubling that seen with Dimethoate.
[0299] The corresponding data on agronomic impact of the treatments (table 2) is consistent with reduction in cabbage root fly damage increasing saleable yield. In the case of ECOguard® the mean increase in saleable yield overall was 15%, with a maximum value of 28% recorded at Toten, consistent with the corresponding significant reduction in cabbage root fly damage at this site.
[0300] A comparison of efficacy in relation to rainfall at Ga-Fa and Toten, the two trials with greatest cabbage root fly attack, shows that the loss of efficacy at Ga-Fa was almost certainly attributable to no rainfall following the first application and very heavy rainfall associated with the second and third applications.
[0301] At Ga-Fa the rainfall recorded for the 14 days covering the second and third treatment was 95.2 mm. In contrast over the same period covering the second and third treatment at Toten, the rainfall was 17.5 mm, falling mostly as light rain.
[0302] The actual rainfall records for both sites are given in table 3 below.
[0000]
TABLE 3
Rainfall comparisons at Toten and Ga-Fa
Toten First treatment 30 Jun. 2004
GaFa First treatment 11 Jun. 2004
Each trial received 3 applications of ECOguard ® granules at
weekly intervals
Ga-Fa
Rainfall
Toten
Rainfall
8 June
0.0
27 June
0.1
9
3.2
28
5.1
10
1.2
29
1.2
11 First application
0.0
30 First application
0.0
12
0.0
1 July
1.7
13
0.0
2
19.4
14
0.0
3
−0.1
15
0.0
4
0.0
16
0.0
5
8.3
17 Second application
0.0
6 Second
2.0
application
18
0.0
7
−0.1
19
9.2
8
0.0
20
13.8
9
−0.1
21
3.8
10
0.1
22
6.8
11
0.1
23 Third application
2.4
12 Third
0.1
application
24
28.8
13
1.0
25
16.2
14
0.0
26
4.0
15
0.0
27
0.0
16
0.0
28
0.0
17
−0.1
29
10.0
18
15.1
30
0.0
19
0.7
20
−0.1
Total rainfall 8-30
99.4
mm
27 June-20 July
55.4
mm
June
Rainfall from second
95.2
mm
Rainfall from
17.5
mm
application to end of
second application
period
to end of period.
Rainfall for four days
4.2
mm
6.3 mm
preceding first
application
[0303] The amounts of rainfall at each site prior to the first treatment were very similar, 4.2 and 6.3 mm. However following the first application, the patterns of rainfall at each site became very different. The 10-day period following the second application is shaded for ease of comparison.
[0304] At Ga-Fa there was no rainfall for 8 consecutive days following the first application, which also covered 2 days in to the second application. Following this, there were 8 consecutive days of uninterrupted rain, with the third application being applied in the middle of this rainfall. The amount of rainfall recorded in this 8 day deluge was 85 mm.
[0305] With the first application at Ga-Fa experiencing totally dry conditions for 8 days and the second and third application then experiencing 8 and 4 days respectively of uninterrupted heavy rain, little if any effect from ECOguard® would have been expected as these represent the extremes of conditions which the inventors believe negatively impact on efficacy. The fact that each treatment experienced one or other of these extremes would completely compromise any impact on cabbage root fly. The data reflects this.
[0306] In contrast, the site at Toten experienced far more settled conditions than Ga-Fa. The first application experienced a heavy rainfall event (19.4 mm) two days after application, which probably impacted negatively on efficacy, but the second and third applications placed towards the centre of the peak of egg laying experienced 11 consecutive days of settled conditions with only very light rainfall (1 mm maximum on any single day). These conditions are considered ideal for maximizing efficacy. The inventors have previously submitted data from laboratory studies that show this. The second and third applications at Toten were therefore expected to have been efficacious.
[0307] The statistical analysis of cabbage root fly damage at Toten showed that both Dimethoate and ECOguard® significantly reduced damage (P=0.004) leading to agronomically meaningful increases in saleable material from the ECOguard® treatment.
[0308] In terms of RDI, Dimethoate and ECOguard® were significantly better than control, but not significantly different to each other.
[0000]
Trt 1 =
Control
Trt 2 =
Dimethoate
Trt 3 =
ECOguard ®
[0309] trt=1 subtracted from:
[0000]
Level
Difference
SE of
Adjusted
trt
of Means
Difference
T-Value
P-Value
2
−0.3100
0.1223
−2.535
0.0302
3
−0.3900
0.1223
−3.190
0.0041
[0310] 2.1 Romedal
[0311] The fifth trial site with swede was harvested earlier than the four other sites introduced in table 1 and 2.
[0312] This site experienced generally light pest pressure, but did include a group of other ECOguard® treatments applied as sprays.
[0313] The data from this trial also produced significant differences in treatments when analyzed by GLIM ANOVA, with all ECOguard® treatments having lower cabbage root fly damage then the control.
[0314] This is shown below
[0315] Kruskal-Wallis Test on C7
[0000]
Trt
N
Median
Ave Rank
Z
1
75
0.00E+00
218.4
2.72
2
75
0.00E+00
175.4
−1.13
3
75
0.00E+00
182.8
−0.47
4
75
0.00E+00
175.4
−1.13
5
75
0.00E+00
188.1
0.01
Overall
375
H = 23.38
DF = 4
P = 0.000 (adjusted for ties)
[0316] All ECOguard® treatments have significantly lower (P=0.000) cabbage root fly damage than the control (trt 1). Treatment 5 is the ECOguard® granule and shows a 14% reduction in overall damage.
[0317] Presentation of the data as root damage index gives a value of 11.6 for control and 4.9 for ECOguard® granules (PSD calculation)
[0318] Although the level of attack at Romedal was low with an RDI of 11.6, a much higher level of attack occurred at Toten, with an RDI of 54.67, (higher than anything noted in controls from the UK field trials in 2004) with both of these sites showing significant reductions in cabbage root fly damage.
[0319] The one common feature at both Romedal and Toten was generally settled conditions associated with the second and third treatment applications. The rainfall data for both Toten and Romedal are presented in table 4.
[0000]
TABLE 4
Rainfall comparisons at Toten and Romedal
Toten
Rainfall
Romedal
Rainfall
30 June first application
0.0
First application
1.7
1 July
1.7
30.2
2
19.4
0.2
3
−0.1
0.0
4
0.0
4.2
5
8.3
4.5
6
2.0
0.0
7 Second application
−0.1
Second application
0.0
8
0.0
0.0
9
−0.1
0.0
10
0.1
0.0
11
0.1
0.2
12
0.1
2.0
13
1.0
0.0
14 Third application
0.0
Third application
0.0
15
0.0
0.0
16
0.0
0.0
17
−0.1
17.9
18
15.1
0.7
19
0.7
0.0
20
−0.1
0.0
21
0.0
Fourth application
0.0
22
0.3
0.7
23
−0.3
0.0
24
33.2
3.3
[0320] Toten and Romedal initiated treatments on the same day in response to detection of the first cabbage root fly eggs. Treatments then followed on a weekly pattern at both sites, with Romedal having one more treatment than Toten. The first, second and third treatments at both sites were therefore synchronous and experienced very similar patterns and intensity of rainfall, which for the period associated with treatments 2 and 3 was very light at both sites.
[0321] As discussed in table 3, this contrasts with the rainfall pattern and intensity at Ga-Fa, which was very heavy and prolonged during the second and third applications.
[0322] The evidence of efficacy at Toten and Romedal appears to be very closely associated with settled conditions and episodes of light rain, with the second and third applications corresponding to a peak in egg laying.
[0323] 3.0 Conclusions
[0324] Non-public field trials on swede in Norway showed ECOguard® granules produced significant reductions in cabbage root fly damage; this was irrespective of the intensity of challenge. Significant differences were seen in data sets with RDI values in the control ranging from 11.9-54.67.
[0325] The trials did not feature factorial additions of product, but it can be clearly inferred from the data on rainfall that the significant effects were largely driven by the second and third treatments being applied during the peak of pest pressure when mostly light rainfall occurred.
[0326] These conclusions are not at variance with those reached from non-public field trials in the UK if misleading trials data is restricted and collectively demonstrate a useful level of product efficacy can be obtained with well-timed applications in appropriate environmental conditions.
[0327] The maximum gain of saleable material, 28%, associated with ECOguard® granule application at Toten is considered commercially significant. In the UK such a gain would equate to ˜11.2 tonnes of material, at a price of ˜£200/tonne, this represents an increased return of ˜£2240/ha.
[0328] The efficacy of the granules is very dependent on moisture and the time of application relative to laying of eggs by cabbage root fly.
[0329] These experiments considered the timing of application of water to granules relative to the time of placement of freshly laid eggs in the bioassay arenas.
[0330] In all two soil types were used with the following treatments replicated 10 times with 10 eggs/assay:-
1. Control (water+Eggs) 2. Granules+eggs 3. Granules+eggs+water added 1 day after eggs 4. Granules+eggs+water added 30 mins after eggs 5. Granules+water+eggs added after 1 day 6. Granules+water+eggs added after 30 mins
[0337] The following results were obtained:-
[0338] Percent of Hatched Eggs
[0000]
TABLE 1
Soil type
Treat. 1
Treat. 2
Treat. 3
Treat. 4
Treat. 5
Treat. 6
Natural
95
81
80
12
59
4
Compost
96
76
39
15
68
18
Mean
95.5
78.5
59.5
18.5
63.5
11
(Treat. = Treatment)
[0339] The following results were obtained:-
[0340] Percent of Hatched Eggs
[0341] These results provide clear evidence that application of water to the granules is vital to enhance efficacy. Treatment 3, which probably most closely resembles the field situation in general, shows that where eggs and granules are present at the base of a plant, followed by a rainfall event, egg hatch is reduced by 38%. This level of efficacy can be greatly enhanced (80% reduction) if the wetting of the granules occurs soon after eggs have been placed (treatment 4). This effect is attributed to the fact that fresh cabbage root fly eggs remain permeable for a few hours after laying and the actives in ECOguard® enter the eggs more readily at this time. It is also implicit from the data above that the timing of application of ECOguard® granules in relation to pest pressure will have a major effect on efficacy (contrast treatments 5 and 6). Applications of product several days after egg laying are likely to be less efficacious that applications of product at the time of egg laying.
EXAMPLE 6
Use of Garlic Concentrate in the Control of Poultry Red Mite
[0342] A garlic concentrate referred to as Breck-a-sol, at 3% v/v (1.5% v Garlic juice concentrate and 1.5% adjuvant oil (rape seed oil)) was applied at a rate of 189 ml/m 2
[0343] FIG. 7 shows results demonstrating the effectiveness of Breck-a-sol (Bsol) against Poultry Red Mite, the percent mortality of red mite is shown against controls and the use of Barricade.
[0000]
Referenced against dry cell
(positive control)
Water
(water control)
Cypermethrin
(1% v/v Barricade (Bcade) at 189 ml/m 2 )
[0344] The results for Breck-a-Sol and Barricade were not significantly different to each other.
[0345] This pattern of data was repeated with five other experiments using mites from different sheds and different batches of garlic juice concentrate.
[0346] Also investigated were the effects of soiling (dust) on efficacy. This work showed useful product efficacy with ‘moderate’ levels of soiling, with efficacy of the garlic concentrate lost only at very high levels of dust soiling.
[0347] In FIG. 8 a series of data is presented comparing the % mortality of poultry red mite under differing levels of soiling when either Breck-a-sol or Barricade (cypermethrin) is applied as a biocide. The results from the application of Barricade are indicated on the key by BC, Dry Con=Dry control, Water=the application of water and the remaining results relate to the application of Breck-a-sol.
[0348] Soiling was applied in incremental loadings to reflect levels of soiling found on surfaces in a poultry shed.
[0349] 0.1 (equivalent to ˜20 g dust/m 2 )
[0350] 0.2 (equivalent to ˜40 g dust/m 2 )
[0351] 0.4 (equivalent to ˜80 g dust/m 2 )
[0352] 0.8 (equivalent to ˜160 g dust/m 2 )
[0353] The results show that the garlic juice concentrate (Breck-a-Sol (Bsol)) delivers a useful level of efficacy when soiling is ˜80 g/m 2 , which was not significantly different to that seen with Barricade applied to soiling at ˜40 gm 2 .
[0354] Appendix 1
[0355] HPLC Analysis
[0356] Chromatogram Data of Various Garlic Oil Samples
[0357] 1. Samples:
A Garlic oil (gold standard) was analyzed together with two other products—a garlic oil (industry standard) and the garlic juice concentrate.
[0359] 2. Sample Preparation:
Both samples were diluted 1:10 with 100% MeCN (50 μl sample in 450 μl MeCN). The garlic juice concentrate produced some white precipitate after dilution. This was removed using a 0.2 μm Target® solvent filter prior to HPLC analysis.
[0361] 3. HPLC Analysis:
This was performed using an Agilent HP1100 HPLC system with diode array detection in combination with a Phenomenex C 18 (2) Luna column (250×4.6 mm, 5 μm) with a ‘Securityguard’ C 18 pre-column. Auto-sampler temperature was 4° C. and the column temperature was 37° C. and cut-off pressure was 280 Bar. Data was collected at 240 nm (with total data collected between 200-600 nm). The injection volume was found to be near optimal at 5 μl for 1:10 diluted samples. Three methods were assessed.
i. One based on a literature method (see below)—with the following modifications—Luna column and isocratic gradient of 70% MeCN (97% MeCN with 3% THF) and 30% ultra-pure water. Method time=40 min. (RBSULF1) ii. A second method—essentially as above but using a pre-gradient step before the isocratic step. (RBSULF2)
[0000]
% B (97% MeCN/3%
Time
% A (Ultra Pure Water)
THF)
0
70
30
10
30
70
35
30
70
40
70
30
50
70
30
iii. A third method (RBSULF3) based on RBSULF1 but with an extended equilibration time i.e. method time=50 min.
[0366] Method Ref:
[0367] Lawson, L. D., Wang, Z-Y. J., Hughes, B. G. (1991). Identification and HPLC quantification of the sulfides and dialk(en)yl thiosulfinates in commercial garlic products. Planta Medica 57: 363-370
[0368] Results: All Chromatograms at 240 nm
A. Separation RBSULF3 Garlic Standard (5 μl 1:10) Raw Data for Garlic Samples Garlic Oil Gold Standard 2.5 μl injection (1:10 diluted oil)—Used as Retention Time and Peak Shape Reference Material
[0373] See FIG. 9 (Chromatogram 1)
[0374] Peak ID
[0375] (The following assignments have been made to the peaks of the chromatograms)
[0000]
1 =
Methyl Allyl Sulfide
CH 3 —S—CH 2 —CH═CH 2
Dimethyl Disulfide
CH 3 —S—S—CH 3
2 =
Methyl Allyl Disulfide
CH 3 —S—S—CH 2 —CH═CH 2
3 =
Diallyl Sulfide
CH 2 ═CH—CH 2 —S—CH 2 —CH═CH 2
4 =
Dimethyl Trisulfide
CH 3 —S—S—S—CH 3
5 =
Diallyl Disulfide
CH 2 ═CH—CH 2 —S—S—CH 2 —CH═CH 2
6 =
Methy Allyl Trisulfide
CH 3 —S—S—S—CH 2 —CH═CH 2
7 =
Dimethyl Tetrasulfide
CH 3 —S—S—S—S—CH 3
8 =
Trans-1-Propenyl Disulfide
CH 2 ═CH—CH 2 —S—S—H
9 =
Diallyl Trisulfide
CH 2 ═CH—CH 2 —S—S—S—CH 2 —CH═CH 2
10 =
Methyl Allyl Tetrasulfide
CH 3 —S—S—S—S—CH 2 —CH═CH 2
11 =
Dimethyl Pentasulfide
CH 3 —S—S—S—S—S—CH 3
12 =
Trans-1-Propenyl Trisulfide (Putative)
CH 2 ═CH—CH 2 —S—S—S—H
13 =
Diallyl Tetrasulfide
CH 2 ═CH—CH 2 —S—S—S—S—CH 2 —CH═CH 2
14 =
Methyl Allyl Pentasulfide
CH 3 —S—S—S—S—S—CH 2 —CH═CH 2
15 =
Dimethyl Hexasulfide
CH 3 —S—S—S—S—S—S—CH 3
16 =
Diallyl Pentasulfide
CH 2 ═CH—CH 2 —S—S—S—S—S—CH 2 CH═CH 2
17 =
Methyl Allyl Hexasulfide
CH 3 —S—S—S—S—S—S—CH 2 —CH═CH 2
18 =
Dimethyl Heptasulfide
CH 3 —S—S—S—S—S—S—S—CH 3
19 =
Diallyl Hexasulfide
CH 2 ═CH—CH 2 —S—S—S—S—S—S—CH 2 —CH═CH 2
[0376] See FIG. 10 (Chromatogram 2-Garlic Standard)
[0377] See FIG. 11 (Chromatogram 3-Garlic Juice Concentrate)
[0378] Peak numbers are provisional. ID's based on the profile shown in the reference paper—there are several additional compounds in the standard and garlic juice concentrate that may be related compounds.
[0379] Samples: Table 2 a. Summary Table of Product Data for a number of batches of the Garlic Concentrate
[0380] (Each compound Expressed as μg Di-Allyl Sulfide Equivalent g −1 Product)
[0000]
Batch
9381
0091
1131
0391
0301
Peak
Thick
Thick
Thick
Thick
Thick
No
Liquid
Liquid
Liquid
Liquid
Liquid
1
82
66
76
55
82
2
131
136
153
104
93
3
87
66
109
104
104
4
579
579
546
409
442
5
841
791
1103
1026
1037
6
846
797
824
693
917
7
T
T
136
115
153
8
T
T
82
55
115
9
4241
3886
4181
4460
3450
10
360
448
415
289
464
11
T
T
T
T
T
12
T
T
T
T
T
13
1916
2233
1971
1643
1676
14
38
55
44
44
22
15
71
87
87
87
49
16
502
731
546
415
480
17
131
191
104
87
115
18
142
262
158
109
164
19
71
120
71
44
71
Total
10038
10448
10606
9739
9434
As % of
Total
DAS
0.9
0.6
1.0
1.1
1.1
(3)
DADS
8.4
7.6
10.4
10.5
11.0
(5)
DATS
42.2
37.2
39.4
45.8
36.6
(9)
3 + 5 + 9
51.5
45.4
50.8
57.4
48.7
[0381] Appendix 2—Fate and Behaviour of the Garlic Concentrate in the Environment
[0382] The formulation of the Ecoguard® granule contains 45% of garlic juice concentrate (AIL 0021) mixed with 55% of wood fibre and cellulosic binder. By far the largest component in the garlic juice concentrate (AIL 0021), the technical product, is carbohydrate. AIL 0021 is believed to comprise upto 50% carbohydrate by weight in the final product. This composition therefore produces a granule with a total composition of a 77.5% w/w mixture of biodegradable and soluble carbohydrate and cellulose.
[0383] The composition of organo-sulphur molecules in the garlic juice concentrate is predominantly molecules with di-sulphur bridges such as diallyl-disulphide and diallyl-trisulphide believed to be in the range 3.5% w/w. These are naturally occurring compounds found in any crushed garlic.
[0384] The biological effects of the garlic juice concentrate, seen in experimentation, has not been attributed to any particular molecule or group of molecules. The biological effects noted have been attributed to the action of the product as a whole. In discussions on the general chemistry of garlic, the emphasis was on identification and quantification of some of the organo-sulphur molecules present as a means of establishing and demonstrating consistency of product during manufacturing.
[0385] The inventors believe that the residue from ECOguard® granules made from garlic juice concentrate (AIL 0021) is predominantly a mixture of biodegradable carbohydrate and cellulose derived from the woodfibre and binder carrier matrix and from pulverization and filtration of whole fresh garlic cloves, with any organo-sulphur residue of coming from approximately 3.5% w/w of organo-sulphur compounds.
[0386] It is believed that the following arguments apply with reference to:-
[0387] Water (degradation and sedimentation/water partitioning
[0388] Soil (degradation and mobility)
[0389] Air
[0390] The minor constituents of the garlic juice concentrate (AIL 0021) such as the organo-sulphur metabolites are characterized by molecules with di-sulphur bridges, which are chemically labile tending to react as electophiles, seeking out nucleophilic functional groups such as —NH 2 ; —SH; —OH; >C═O. Reaction with these functional groups breaks the di-sulphide bridge, which in the case of an aqueous reaction environment produces hydrated sulphur containing functional groups such as:- —R—S—OH, where R represents one half of the di-sulphur bridge.
[0391] More specifically, HPLC analytical work on characterization of the garlic juice concentrate (CL AIL 0021), has shown that four of the principal molecular species are:- di-allyl sulphide; di-allyl disulphide; di-allyl trisulphide and di-allyl tetrasulphide. This is consistent with the breakdown of allicin to diallyl mono, di and trisulphide reported to occur at room temperature by Block 1992 .
[0392] In addition, there is a high degree of similarity between the organo-sulphur chemistry of garlic and onions. Block 1992 reports, “Pioneering studies in the 1940's by Stoll and Seebeck in Basel demonstrated that the stable precursor of Cavallito's antibacterial principle of garlic (allicin) is (+)-S-2-propenyl-L-cysteine-S-Oxide (alliin). In the intact cell, alliin and related S-alk(en)yl-L-cysteine-S oxides (aroma and flavour precursors) are located in the cytoplasm and the C—S lyase enzyme allinase in the vacuole. Disruption of the cell results in release of allinase and subsequent alpha and beta-elimination of the S-oxides, ultimately affording volatile and odorous low molecular weight organo sulphur compounds such as allicin, which readily equilibrates to diallyl-disulphide and other sulphur bridged alkenes.”
[0393] Four sulphoxides occur in Allium spp
[0394] 1 S-2-propenyl-cysteine S-oxide
[0395] 2 S-(E)-1-propenyl-cycteine S-oxide
[0396] 3 S-methyl-cycseine S-oxide
[0397] 4 S-propyl-L-cysteine S-oxide
[0398] Onions contain 2, 3 and 4. Garlic contains 1, 2, and 3.
[0399] There is therefore a high degree of equivalence in the organo-sulphur chemistry between onions and garlic. In the case of onions the action of onion allinase on the precursors leads to dipropyl polysulphides as opposed to diallyl polysulphides, which dominate in garlic.
[0400] Diallyl-sulphides are considered by the inventors to be the major organo-sulphur molecules in the garlic juice concentrate (CL AIL 0021 product); this is consistent with the literature and detailed analytical results. The average concentration of diallyl-disulphide (DADS) in CL AIL 0021 calculated from 5 production batches is 12 mg/g. This therefore gives a theoretical concentration DADS in a typical Ecoguard® granules of 0.54%
[0401] The actual percentage of DADS in an Ecoguard® granule is 0.54% and for DASn 3.46%. Therefore, a 12 kg/ha application of Ecoguard® granules, applies a maximum of 65 g of diallyl-disulphide/ha and 415 g/ha DASn. It is reported by Block 1992 , that garlic, onion and other members of the Allium spp. contain 1-5% dry weight of non-protein sulphur amino acid secondary metabolites. Given that a garlic crop may yield 20 tons/ha fresh weight and that 25% of this is dry matter, then a typical commercial crop of garlic will yield between 50-250 kg of non-protein sulphur that is to say 100-500 times more than with an application of Ecoguard® garlic granules.
[0402] On a simple gravimetric analysis a single Ecoguard® application will apply 100-500 times less organic sulphur than that which could be released into the environment from a commercial crop, if the crop was abandoned to rot down.
[0403] Given the large area of onions grown in the UK and the relative yield per hectare, Onions are a potentially much more significant source of sulphenic acids and polysulphides than garlic.
[0404] The wastage of onions at harvest is considered by the British Onion Producers Association (BOPA) to be about 12% of gross yield, which at 40 tons/ha is about 4.8 tons, this is composed of onions less than 50 mm in diameter that fall through harvesting webs. This trash will be left in the field and disked over to rot. Under these circumstances there will be a substantial release of organo-sulphur molecules into the environment. According to Block 1992 this figure could be as much as 5% of the dry matter or 60 kg/ha. In the year 2,000, around 9,000 ha of onions were grown in the UK with the total trash left in fields being estimated at 40,000 T or about 500 T of organo-sulphur compounds!
[0405] In addition BOPA estimate an additional 50,000 tonnes of onion waste per annum is generated by packers and processors, generating up to 625 T of additional organo-sulphur compounds, most of which will be disposed of to landfill, composting in waste heaps at field boundaries or by incineration again generating a similar rate of release of organo-sulphur compounds.
[0406] In each of these instances the compounds are broken down in the environment by natural processes, such as microbiological degradation, photolysis and bond cleavage by a range of electrophylic functional groups. The garlic residues in the Ecoguard® granules would be broken down by the same processes.
[0407] The inventors therefore conclude that the application of Ecoguard® granules to soil at recommended rates and by recommended methods releases significantly less organo-sulphur molecules to the soil surface than normal agricultural and food processing practices involving garlic, onion and other allium crops and that as there are no noticeable effects on the environment from the aforementioned standard practices then the fate in the environment issue need not be addressed in any greater detail. The same arguments also apply to the direct use of the garlic juice concentrate. | A method of treating an individual with a condition which condition is one wherein the individual with the condition benefits from the administration of GnRH and/or a GnRH analogue, the method comprising administering to the individual GnRH and/or a GnRH analogue and an inhibitor of prostaglandin synthesis and/or a prostaglandin receptor antagonist. The methods of the invention also include combating a sex-hormone dependent disease in an individual, and regulating fertility in an individual. | 0 |
[0001] This invention relates to a novel ultra-thin fiber Textured Yarn with elastic characteristics and its manufacturing method. Specifically, this invention relates to a novel elastic ultra-thin fiber Textured Yarn manufactured by concurrently feeding spun ultra-thin fiber Textured Yarn and spun thermoplastic fiber into a compression air jet system and passing the resulting product through wire feed and winding rollers.
[0002] Republic of China's Patent No. 127812 entitled “the manufacturing method of iso-shrinkage ultra-thin fiber Textured Yarn” teaches a traditional method for manufacturing ultra-thin fiber. Ultra-thin fiber Textured Yarn with boiling water shrinkage below 10% and high shrinkage low crimpled gray yarn with boiling water shrinkage above 15% are compounded and processed to form a single yarn unit. Fabrics manufactured using yarns made with such a traditional method have thick feel and noticeable stiffness, which are appreciated by visual examination of the draped fabrics. However, these fabrics lack elasticity and are not comfortable when worn.
[0003] In response to thick feel, stiffness and lack of comfort associated with fabrics produced using traditional methods such as the method discussed above, and in order to produce yarn with elastic covering characteristics, manufacturers often wrap the produced yarn around a Spandex (trade name for a type of polyurethane elasticity silk) periphery to form a single/dual wrapped yarn. Additionally, the produced yarn is knobbed with high speed air and wrapped around the periphery of a LYCRA Spandex to produce elastic covering yarn. Although such Spandex-based yarns have elasticity, production of the latter involve complex manufacturing procedures and high manufacturing cost. The following shortcomings are clear noticeable:
[0004] 1. Higher manufacturing cost due to technical complexity associated with raw materials.
[0005] 2. Higher manufacturing cost due to technical complexity associated with the manufacturing process.
[0006] 3. Process not applicable to high temperature dyeing and finishing; and easy coloring embrittlement results due to moist heat intolerance.
[0007] 4. Alkali (NaOH) intolerant decrement processing.
[0008] 5. Uneasy tension control exist during the opening of band yarn and during finish processing, which is caused by unwanted elasticity and reduced product quality; and industrial processing efficiency is negatively influenced due to extreme process difficulties.
[0009] It is an object of this invention to solve the shortcomings associated with Spandex-based yarns production and other traditional methods of producing yarns with elastic covering characteristics.
[0010] Another object of this invention is to produce high-class yarn with elastic function by false twisting thermoplastic fiber with self-winding elasticity characteristics into ultra-thin fiber via a compression air jet system.
[0011] Still another object of this invention is to simplify the process of manufacturing elastic complex yarns and to reduce the cost associated with producing elastic complex yarns. Still further, another object of this invention is to manufacture elastic complex yarns with excellent size stability, capable of being easily woven, suitable for the textile and slopwork industries, and capable of producing textiles with good elasticity and high degree of comfort.
SUMMARY OF THE INVENTION
[0012] This invention discloses a method for manufacturing novel ultra-thin fiber Textured Yarn with elastic characteristics. The process involves blending ultra-thin fiber Textured Yarn with thermoplastic fiber having self-winding characteristics.
[0013] The ultra-thin fiber Textured Yarn of this invention is manufactured by heating, false twisting and spinning of continuous long fiber using traditional or compound spinning methods. The thermoplastic plastic of this invention is manufactured by spinning two thermoplastic polymers with different shrinkage. The ultra fiber Textured Yarn and the thermoplastic fiber are concurrently fed into a compression air jet and compounded into the elastic ultra-thin fiber yarn of this invention. Finally, the produced elastic ultra-thin fiber processing yarn is fed through wire feed rollers and subsequently wrapped with winding rollers.
BRIEF DESCRIPTION OF THE DRAWINGS
[0014] [0014]FIG. 1: Shows a compound false-twist processing flow sheet for manufacturing elastic ultra-thin fiber processing yarn. The equipment symbols associated with the flow sheet are as follows: ( 1 ) Silk guide; ( 2 ) First wire; ( 3 ) Heater; ( 4 ) Cooling plate; ( 5 ) Friction ingot group; ( 6 ) Silk guide; ( 7 ) Second wire feed roller; ( 8 ) Compression air jet system; ( 9 ) Third wire feed roller; ( 10 ) Elastic ultra-thin fiber processing yarn; and ( 11 ) Batch roller.
[0015] [0015]FIG. 2: Shows a self-winding elastic thermoplastic fiber used for manufacturing the elastic ultra-thin fiber yarn of this invention. The figure shows the configuration of two thermoplastic polymers of different shrinkages into a fiber cross section constituting both polymers.
DETAILED DESCRIPTION OF THE INVENTION
[0016] This invention discloses novel Ultra-thin Fiber Textured Yarn with elastic characteristics and its manufacturing method. Specifically, this invention relates to novel elastic ultra-thin fiber Textured Yarn manufactured by concurrently feeding spun ultra-thin fiber Textured Yarn and spun thermoplastic fiber into a compression air jet system and passing the resulting product through wire feed and winding rollers.
[0017] The ultra-thin fiber Textured Yarn of this invention is obtained by heating, false twisting, and post processing of continuous long fiber woven with general-synthetic fiber by using traditional spinning or compound spinning methods to produce a yarn whose filament size is below 0.5 denier. The traditional spinning method, which usually occurs after a false twisting process, uses a single polymer under traditional conditions and with traditional equipment to spin out continuous long fiber yarn whose filament size is below 0.5 denier. The continuous long fiber yarn is subsequently false twisted and processed into Ultra-thin fiber Textured Yarn whose filament size is below 0.5 denier. In contrast, the compound spinning method, which usually occurs after a false twisting process, uses two different polymers under traditional conditions and with traditional equipment to spin out continuous long fiber yarn whose filament size is below 0.5 denier. The continuous long fiber yarn is subsequently false twisted and processed into Ultra-thin fiber Textured Yarn whose filament size is below 0.5 denier.
[0018] The second material used to manufacture the invention of this patent application is thermoplastic fiber with self-winding elastic characteristics. The thermoplastic fiber is obtained by configuring two thermoplastic polymers of different shrinkages into a fiber cross section by spinning with a compound spinneret having the desired proportionality. The different contraction stresses between the interfaces of the two thermoplastic polymers with different shrinkages form spring-like screw and generate self-winding elasticity. See the manufacturing diagram shown in FIG. 2.
[0019] To form the ultra-thin fiber Textured Yarn with elastic characteristics of this invention, thermoplastic fiber with self-winding elastic characteristics and continuous long fiber are first individually spun using traditional spinning methods or compound spinning methods. Specifically, the continuous fiber is false twisted, spun, heated, subsequently false twisted and post processed into a ultra-thin fiber Textured Yarn whose filament size is below 0.5 denier. The ultra-thin fiber Textured Yarn produced from the continuous long fiber and the thermoplastic fiber is compounded to form an in-process Textured Yarn. The in-process Yarn is passed through a weaving process, a dyeing process and a finishing process. The high in-process temperature is utilized to generate shrinkage difference within the thermoplastic fiber thereby inducing elastic characteristics in the final product.
[0020] The manufacturing process steps of this invention are summarize as follows: ultra-thin fiber Textured Yarn is manufactured by heating, false twisting and spinning of continuous long fiber using traditional or compound spinning methods; separately, thermoplastic fiber with self-winding characteristics is manufactured by spinning two thermoplastic polymers with different shrinkage after first being melted and spun using a compound spinneret of desired proportion; the ultra fiber Textured Yarn and the thermoplastic fiber are concurrently fed into a compression air jet are compounded into elastic ultra-thin fiber processing yarn; and the resulting elastic ultra-thin fiber processing yarn is passed through wire feed rollers and wrapped with winding rollers.
[0021] Referring to FIG. 1 for additional clarification of the manufacturing process steps of this invention, ultra-thin fiber spinning cake (A) is relaxed via silk guide ( 1 ), and passed through a first wire feed roller ( 2 ). The resulting ultra-thin fiber product is heated with a heater ( 3 ), passed over a cooling plate ( 4 ) and through a friction ingot group ( 5 ). The ultra-thin fiber product is then passed through a second wire feed roller ( 7 ) to form the Textured Yarn. Steps 1 - 7 are the heating, extending, curl reshaping and cooling processes required to produce the ultra-thin Textured Yarn material of this invention.
[0022] Still referring to FIG. 1 of the inventive process, at the moment the ultra Textured Yarn is fed through the second wire rollers ( 7 ), self-winding thermoplastic fiber (B) is incorporated into the ultra Textured Yarn through the silk guide ( 6 ), and combined with the Textured Yarn and fed into a compression air jet system ( 8 ) with air nozzle supplied with a considerable amount of pressure. The ultra-thin Textured Yarn and the thermoplastic fiber are compounded into an elastic ultra-thin fiber processing yarn ( 10 ) and guided by a third wire feed roller ( 9 ) down stream. Finally, the elastic yarn with feed rate controlled by the third feed roller ( 9 ) and the winding roller ( 11 ) is produced.
[0023] Still referring to FIG. 1 of this invention, the friction ingot group ( 5 ) is not restricted to any one type or any one combination. All well-known ingot groups such as friction disc, friction belt, and pin ingot, etc. are applicable. The air nozzle of the compression air jet system ( 8 ) is not restricted to any one type or any one combination. All well-known nozzles, such as ordinary nozzle and mixed fiber nozzle etc. are applicable. To achieve the maximum integration of the thermoplastic fiber into the ultra-thin Textured Yarn to form a compound (elastic ultra-thin fiber) with good reliability, the number of processed yarn shall be over 85 sections/m.
[0024] The elastic ultra-thin fiber processing yarn ( 10 ) of this invention can be woven into cloths and textiles of various shapes. Due to the elastic effect demonstrated prior to hot water treatment no problem of pull control exists; therefore, various shapes can be obtained through knitter, shuttle and shuttle less loom. The weaving and quality characteristics of this invention are superior to contemporaneous elastic yarn complexes. By manufacturing the elastic yarn with thermoplastic polymers interface having two different shrinkage, which forms spring-like screw due to the difference in shrinkage stress when exposed to high temperature during post processing, textiles produced using this invention demonstrated excellent elasticity and a high degree of comfort.
[0025] By way of examples of exploitation/comparison and explanation, the evaluation method, the manufacturing processes, conditions and process components, though not limited to the exploitations, of the present invention may be as follows:
[0026] Explanation of Elasticity Evaluation Method
[0027] Workbench: INSTRON—6021 universal tensile testing machine
[0028] Method:
[0029] a. Tailor 2.5 cm×30 cm test piece under the condition of room temperature without tension (Containing clamping section 10 cm).
[0030] b. Test rate for 1.667 mm/Sec Return speed for 10.0 mm/Sec
[0031] c. Test piece pre-load 12 g
[0032] d. Fixed pull of 1000 g
Calculation: elastic extension (fixed pull 1000 g)=( A 2 −A 1)÷ A 1×100%
[0033] A1: Test piece length before stretching
[0034] A2: Test piece length applying fixed pull 1000 g
[0035] (Example of Exploitation)
[0036] 360d/48f polyester, an upgraded polyester compound, ultra-thin fiber spinning cake (A) is relaxed via silk guide ( 1 ), and passed through a first wire feed roller ( 2 ) The ultra-thin fiber product is heated to 160° C. with a heater ( 3 ) (having a temperature range between 100-200° C.). The resulting product is passed over a cooling plate ( 4 ), false twisted by passage through a friction ingot group ( 5 ) and extended to 2.28 times with the second wire feed roller ( 7 ) (having an extension multiple of between 1.3-4.0), to form the Textured Yarn. At the moment the ultra-thin Textured Yarn is fed through the second wire roller ( 7 ), 75d/24f spun polyester, self-winding elastic fiber (B) is incorporated into the second wire feed roller ( 7 ) via silk guide ( 6 ) at speed of 500 m/minute (the second wire feed roller speed range is between 300-900 m/minute). The resulting product is combined with the Textured Yarn and fed into the air jet compression system ( 8 ) with air nozzle having air pressure of about 50 kg/m 2 , at the guiding end of the yarn. The ultra-thin Textured Yarn and the thermoplastic fiber are compounded into an elastic ultra-thin fiber processing yarn ( 10 ) and guided by a third wire feed roller ( 9 ) down stream.
[0037] A 225d/72d elastic ultra-thin elastic yarn with feed rate controlled by the third feed roller ( 9 ) and the winding roller ( 11 ) is produced consistent with the process flow chart shown in FIG. 1. The processed yarn is used as filling, wrapped with 75d/36f Textured Yarn, weaved and reduced by 25%. Post processing such as burring, dyeing to produce cloth of enhanced thickness, drape, wax, particularity, peach skin feeling and elastic extension (fixed pull 1000 g) that reaches 23.1% were performed. Clothing produced using this exploitation maintained a high degree of comfort when worn.
EXAMPLE OF COMPARISON
[0038] In this example, conditions are similar to the processing conditions above. However, the self-winding elastic thermoplastic fiber (B) is replaced with 45% high shrinkage low crimpled gray yarn having boiling water shrinkage and dimensions of 75d/36f to produce 225d/84f iso-shrinkage ultra-thin fiber Textured Yarn. Similar to the above exploitation, the processed yarn is used as filling, wrapped, weaved and reduced. Post processing such as burring, dyeing to produce cloth of enhanced thickness, drape, wax, particularity, peach skin feeling and elastic extension (fixed pull 1000 g) that reaches only 5.8% were performed. Thus, clothing produced using this example possessed many shortcomings and lack the needed comfort when worn.
[0039] Comparing the example of exploitation with the example of comparison, it is clear that the use of properly processed thermoplastic fiber with self-winding elastic performance and ultra-thin fiber Textured Yarn resulted in the production of unique elastic ultra-thin fiber with enhanced intrinsic performance, as compared with traditional ultra-thin fiber Textured Yarn. | This invention discloses a method for manufacturing ultra-thin fiber yarn having elastic characteristics. Ultra-thin fiber Textured Yarn and thermoplastic fiber are concurrently fed into a compression air jet system to produce elastic ultra-thin fibers. The two materials are made into a novel yarn with elastic function using the process of this invention, which is simpler as compared with other traditional processes associated with manufacturing elastic complex yarn. The process of this invention is capable of manufacturing elastic complex yarns with excellent size stability, capable of being easily woven, suitable for the textile and slopwork industries, and capable of producing textiles with good elasticity and high degree of comfort. | 3 |
SUMMARY OF THE INVENTION
The invention is directed to a Nα-(3-cyanopropanoyl)-aminocarboxylic acid derivatives of the general formulae ##STR1## wherein R 1 is hydrogen, methyl, ethyl, or benzyl, n is 2, 3, or 4 and R 2 is hydrogen or one of the following groups: ##STR2## Nα-(3-cyanopropanoyl)-aminocarboxylic acid derivatives of general formulae (I) and (II) are valuable intermediate products for the production of pharmaceuticals. Schiff bases of the aminobutyramide derivatives, prepared by reducing the cyanopropionamide derivatives of the invention and subsequent conversion to the azomethines, have the same uses as those disclosed for the Gabamid derivatives in German Auslegeschrift No. 26 34 288. The hydrochloride salts of the 4-aminobutyramide derivatives also can be used as catalysts for the curing of urea-formaldehyde and melamine-formaldehyde resins, e.g. when used in an amount of 0,1 to 5% of the resin. A further object of the invention therefore ist the use of the Nα-(3-cyanopropanoyl)-aminocarboxylic acid derivatives of the general formulae (I) and (II) for the production of derivatives of 4-aminobutyramide by reduction.
The compounds of the invention can be produced by various processes:
Process A:
3-Cyanopropionic acid is reacted with the appropriate a-aminocarboxylic acid or its methyl, ethyl, or benzyl ester in the presence of a coupling agent, such as dicyclohexylcarbodiimide. Thereby there can be employed as solvents halohydrocarbons such as dichloromethane, chloroform, or carbon tetrachloride; ethers such as diethyl ether, diisopropyl ether, methyl-tert.-butyl ether, dioxane, or tetrahydrofuran; nitriles such as acetonitrile; or aromatic hydrocarbons such as benzene or toluene. The reaction suitably takes place at a temperature between -20° and +20° C., preferably between -10° and +10° C.
Process B:
3-Cyanopropionic acid is first converted into its anhydride or a mixed anhydride, for example with acetic acid, or into the corresponding acid chloride or activated by means of the Woodward-Reagent K, N-ethoxycarbonyl-2-ethoxy-1,2-dihydroquinoline and then reacted with the appropriate α-aminocarboxylic acid or its methyl, ethyl, or benzyl ester. Thereby it is advantageous to have present a base, for example, caustic soda or a tertiary amine such as pyridine, 4-(dimethylamino)-pyridine or triethylamine.
A review of known acylation processes which can be used in the present connection is contained in Houben-Weyl, Methoden der Organischen Chemie, Vol. XV, Part II, (1974), pages 1 et seq.
In a preferred illustrative form of Process B the 3-cyanopropionic acid is converted by reaction with thionyl chloride or oxalyl chloride into the corresponding acid chloride and this reacted in the presence of aqueous sodium hydroxide with the α-aminocarboxylic acid or its ester. The reaction takes place suitably at a temperature between -20° and +50° C., preferably between -20° and +30° C.
Process C:
3-Cyanopropionic acid esters of the general formula ##STR3## in which R 3 is a straight or branched alkyl group having 1 to 6 carbon atoms is reacted with the appropriate α-aminocarboxylic acid or its methyl, ethyl, or benzyl ester. The reaction takes place under heating, preferably under reflux. It can be carried out in the absence of an additional solvent or in the presence of such solvent, for example, of benzene, toluene, or xylene.
Process D:
Nα-acryloyl-aminocarboxylic acid derivatives of the general formulae ##STR4## in which R 1 , R 2 , and n are as defined above are reacted with hydrocyanic acids in such manner than the HCN adds on to the double bond of the acrylic acid residue. The addition takes place especially smoothly in the presence of catalytic amounts of an alkali metal cyanide, for example, sodium or potassium cyanide. As solvent for this reaction there can be employed, e.g. dimethyl formamide, diethyl formamide, dimethyl acetamide, N-methyl pyrrolidone, tetrahydrofuran, dimethyl sulfoxide, tetramethylene sulfone (sulfolane) or tetramethyl urea and its homologues with up to 8 carbon atoms. The reaction suitably takes place at a temperature between 20° and 150° C., preferably between 70° and 120° C. The pressure has no detectable influence on the speed of reaction and the composition of the reaction mixture after the end of the reaction. The reaction advantageously can be carried out in such manner that there is present a suspension of the catalyst in a portion of the solvent and there is slowly fed in a solution of the Nα-acryloyl-amino-carboxylic acid derivative of the general formula (IV) or (V) and the hydrocyanic acid in the remainder of the solvent. However, just as well there can also be present a solution of the Nα-acryloyl-aminocarboxylic acid derivative in which the catalyst is suspended and the hydrocyanic acid led in.
In all of the above-mentioned processes A, B, and C insofar as the α-aminocarboxylic acid or its ester contains besides the α-amino group, a further amino group or a hydroxyl group this amino or hydroxyl group naturally must be protected according to the known methods of peptide chemistry, for example, through a benzyloxycarbonyl or tert.-butyloxycarbonyl group.
The Nα-acryloyl-aminocarboxylic acid derivative employed in the above Process D can be obtained from the α-aminocarboxylic acid or its esters through reaction with acrylic acid chloride or methacrylic acid chloride according to the Schotten-Baumann reaction. In this reaction too it is understood that any further amino group or hydroxyl groups present in a given case must also be protected through a protective group.
Examples of compounds of general formula (I) according to the invention are N-(3-cyano-propanoyl)-azetidine carboxylic acid, N-(3-cyano-propanoyl)-proline, N-(3-cyano-propanoyl)-pipecolic acid, as well as their methyl-, ethyl-, and benzyl esters.
Examples of compounds of general formula (II) according to the invention are N-(3-cyano-propanoyl)-glycine, N-(3-cyano-propanoyl)-alanine, N-(3-cyano-propanoyl)-valine, N-(3-cyano-propanoyl)-isoleucine, N-(3-cyano-propanoyl)-leucine, N-(3-cyano-propanoyl) methionine, N-(3-cyano-propanoyl)-phenylalanine, N-(3-cyano-propanoyl)-O-acetyl-tyrosine, N-(3-cyanopropanoyl)-O-(benzyloxy-carbonyl)-threonine, N-(3-cyano-propanoyl)-O-(tert.-butyloxycarbonyl)-serine, Nα-(3-cyano-propanoyl)-Nε-(benzyloxycarbonyl)-lysine, Nα-(3-cyano-propanoyl)-histidine, Nα-(3-cyano-propanoyl)-N-methyl-histidine, as well as their methyl-, ethyl-, and benzyl esters.
The α-aminocarboxylic acids, except glycine, taken as a basis of the compounds of the invention can be present in the D-form, in the L-form or as the racemate.
Derivatives of 4-amino-butramide can be produced suitably from the Nα-(3-cyanopropanoyl)-aminocarboxylic acid derivatives of general formula (I) or (II) by hydrogenating them in the presence of a solvent inert under the reaction conditions, a noble metal catalyst and hydrogen chloride at a temperature between 0° and 150° C. Insofar as R 2 in general formula (II) signifies a protective group, normally in the hydrogenation the protective group is also split off so that there is obtained a 4-aminobutyramide which also exhibits a further free functional group.
Generally in the hydrogenation first there is formed the hydrochloride of the 4-aminobutyramide derivative which in a given case in a very simple manner, e.g. by treatment with a basic ion exchange resin or with a suitable base, can be converted into the free 4-aminobutyramide derivative.
The hydrogenation takes place in the presence of a solvent inert under the conditions of the hydrogenation reaction. Suitable solvents are water, primary or secondary alcohols having up to 6 carbon atoms, preferably 1 to 3 carbon atoms or their mixtures with each other or with water. The amount of solvent employed is not critical, however, suitably it should be so regulated that the Nα-(3-cyanopropanoyl)-aminocarboxylic acid derivative employed is completely dissolved at the reaction temperature chosen. Especially preferred solvents are water, methanol, ethanol or isopropyl alcohol. Furthermore, the hydrogenation requires the presence of a noble metal catalyst, e.g. palladium, rhodium, or especially a platinum metal catalyst. Especially preferred catalysts are metallic platinum and platinum IV oxide. There can also be employed just as well mixtures of several noble metals or mixtures of noble metals with platinum IV oxide. The catalysts can be used in the free form or as catalysts on carriers (e.g. precipitated on activated carbon). After the end of the hydrogenation they can be recovered and again employed without further purification, whereby in the case of platinum IV oxide it is unimportant whether this is present after the first use partially or completely reduced to Pt 2+ compounds or metallic platinum. The amount of noble metal catalyst employed is not critical. However, it is recommended for obtaining shorter hydrogenation times to employ the noble metal catalysts in such amount that the weight ratio between the Nα-(3-cyanopropanoyl)aminocarboxylic acid derivative employed and the catalyst is from 300:1 to 1:1, preferably 100:1 to 5:1.
Finally the hydrogenation takes place in the presence of hydrogen chloride, which suitably is used in equimolar amount to the Nα-(3-cyanopropanoyl)-aminocarboxylic acid derivative employed. However, the use of a slight excess of hydrogen chloride is also possible.
The hydrogenation takes place at a temperature between 0° and 150° C., preferably between 10° and 50° C. It can be carried out without pressure (i.e. without superatmospheric pressure) by leading hydrogen through the reaction mixture, or in a pressure resistant reaction vessel under a hydrogen pressure up to 100 bar. Preferably, the hydrogenation takes place at pressures up to 20 bar. The hydrogen pressure to be sure has a certain influence on the time required for the complete hydrogenation which is somewhat shortened with increasing pressure, but has scarcely any influence on the purity of the 4-aminobutyramide derivative formed.
Unless otherwise indicated all parts and percentages are by weight.
The process can comprise, consist essentially of, or consist of the stated steps with the materials set forth.
The invention is further explained in connection with the following examples.
DETAILED DESCRIPTION
EXAMPLE 1
A solution of 26.9 grams (0.15 mole) of L-phenylalanine methyl ester in 200 ml of dichloromethane was treated successively dropwise at 0° C.
(a) with a solution of 30.9 grams of N,N'-dicyclohexylcarbodiimide in 75 ml of dichloromethane and
(b) with a solution of 14.9 grams (0.15 mole) of 3-cyanopropionic acid in 30 ml of dichloromethane. The mixture was allowed to stand overnight and the precipitate which came out was filtered. The filtrate was washed with water, dried, filtered and the solvent removed on a rotary evaporator. The residue was recrystallized from a mixture of ethyl acetate and petroleum ether. There were obtained 26.8 grams (68.6% of theory) of N-(3-cyanopropanoyl)-L-phenylalanine methyl ester. Melting Point: 71°-72° C.
α D 20 =+12.2° (c=4 in Methanol)
Elemental Analysis: C 14 H 16 N 2 O 3 (260.29)
______________________________________ Calculated (%): Found (%):______________________________________C 64.60 65.00H 6.20 5.99N 10.76 10.89______________________________________
IR-Spectrum (neat): ν(--C.tbd.N) 2270 cm -1 .
EXAMPLE 2
26 grams (0.1 mole) of N-(3-cyanopropanoyl)-L-phenylalanine methyl ester were dissolved in 150 ml of ethanol which contained 0.1 mole of hydrogen chloride and hydrogenated with hydrogen in the presence of 0.8 gram of platinum IV oxide at normal pressure and 30° to 35° C. After 11/2 hours the theoretically calculated amount of hydrogen was taken up. The catalyst was filtered off and the filtrate evaporated to dryness. The residue remaining was stirred for 2 hours with 0.2 mole of NaOH in ethanol/water to split off the ester group. In the neutralization to pH6 a colorless precipitate of N-(4-aminobutyryl)-L-phenylalanine crystallized out.
Yield: 19.6 grams (78.4% of theory)
Melting Point: 225°-226° C.
α D 20 =+32.6° (c=1 in water)
The material reacted positive to ninhydrin.
EXAMPLE 3
Example 1 was repeated with the single difference that in place of L-phenylalanine methyl ester there was treated the D-phenylalanine methyl ester.
Yield of N-(3-cyano-propanoyl)-D-phenylalaninemethyl
ester: 26.9 grams (68.9% of theory)
Melting Point: 72°-73° C.
α D 20 =-12.1° (c=4 in methanol)
IR-Spectrum (neat): ν(--C.tbd.N) 2270 cm -1 .
EXAMPLE 4
Example 2 was repeated with the single difference that in place of N-(3-cyanopropanoyl)-L-phenylalanine methyl ester there was employed the D-isomer. There were obtained 20.1 grams (80.4% of theory) N-(4-amino-butyryl)-D-phenylalanine,
Melting Point: 224°-225° C.
α D 20 =-31.9° (c=1 in water)
The material reacted positive to ninhydrin.
EXAMPLE 5
Example 1 was repeated with the single difference that in place of the L-phenylalanine methyl ester there was employed the D,L-phenylalanine methyl ester.
Yield of N-(3-cyano-propanoyl)-D,L-phenylalanine methyl ester: 22.1 grams (56.6% of theory)
Elemental analysis: C 14 H 16 N 2 O 3 (260,29)
______________________________________ Calculated (%): Found (%):______________________________________C 64.60 64.29H 6.20 5.99N 10.76 10.81______________________________________
IR-Spectrum (neat): ν(--C.tbd.N) 2270 cm -1 .
EXAMPLE 6
The procedure was as in Example 1. In place of the L-phenylalanine methyl ester there were employed 24.8 grams (0.15 mole) of L-histidine methyl ester. The Nα-(3-cyanopropanoyl)-L-histidine methyl ester crystallized out together with the N,N-dicyclohexyl urea and after the filtering off was separated from the latter by extraction with warm acetone. The acetone was distilled off. The product was recrystallized from fresh acetone.
Yield: 18.2 grams (48.5% of theory)
Melting Point: 133°-135° C.
IR-Spectrum (neat): ν(--C.tbd.N) 2250 cm -1 ; ν(--COOR) 1730 cm -1 ; ν(--CO--N<) 1650 cm -1 .
EXAMPLE 7
The procedure was as in Example 1. In place of the L-phenylalanine methyl ester there were employed 19.4 grams (0.15 mole) of L-proline methyl ester. Yield of N-(3-cyanopropanoyl)-L-proline methyl ester: 21.5 grams (68% of theory) as a colorless to yellowish oil.
Thin Layer chromatogram (SiO 2 ; Mobile phase n-butanol:glacial acetic acid:water=4:1:1):R F =0.53
IR-Spectrum (KBr): ν(--C.tbd.N) 2245 cm -1 ; ν(--COOR) 1745 cm -1 ; ν(--CO--N<) 1650 cm -1
EXAMPLE 8
Example 2 was repeated with the single difference that in place of N-(3-cyanopropanoyl)-L-phenylalanine methyl ester there was employed 0.1 mole of N-(3-cyanopropanoyl)-L-proline methyl ester.
The yield of N-(4-aminobutyryl)-L-proline.HCl was 12.5 grams (52.9% of theory). The material is positive to ninhydrin. In the IR spectrum (KBr) there was no longer detectable a nitrile band.
EXAMPLE 9
Example 7 was repeated with the single difference that in place of the L-proline methyl ester there was employed the same amount by weight of the D-proline methyl ester. Yield of N-(3-cyanopropanoyl)-D-proline methyl ester: 23.0 grams (73% of theory).
Thin layer chromatogram (SiO 2 ; mobile phase=n-butanol:glacial acetic acid:water=4:1:1):R f =0.53.
EXAMPLE 10
The procedure was as in Example 1. In place of L-phenylalanine methyl ester there were employed 55.6 grams (0.15 mole) of Nε-(benzyloxycarbonyl)-L-lysine benzyl ester. The oily residue remaining after the evaporation of the dichloromethane crystallized out in triturating with diethyl ether/petroleum ether.
Yield of Nα-(3-Cyano-propanoyl)-Nε-(benzyloxycarbonyl)-L-lysine-benzyl ester: 45 grams (66.7% of theory)
Melting Point: 41°-43° C.
α D 20 =-18.7° (c=2 in methanol)
IR-Spectrum (neat): ν(--C.tbd.N) 2245 cm -1 ; ν(--COOR) 1740 cm -1 (broad); ν(--CO--N<) 1685 and 1655 cm -1 .
EXAMPLE 11
The procedure was as in Example 10 with the single difference that in place of the Nε-(benzyloxycarbonyl)-L-lysine benzyl ester there was employed 55.6 grams (0.15 mole) of Nε-(benzyloxycarbonyl)-D-lysine-benzyl ester.
Yield of Nα-(3-cyano-propanoyl)-Nε-(benzyloxycarbonyl)-D-lysine-benzyl ester: 49.5 grams (73.4% of theory)
Melting Point: 42°-44° C.
α D 20 =+18.6° (c=2 in methanol).
The entire disclosure of German priority application No. P 3124091.7 is hereby incorporated by reference. | There are prepared specific α-aminocarboxylic acids or their methyl, ethyl, or benzyl esters in which the α-amino group is substituted by a 3-cyanopropanoyl group. The compounds are useful for producing the corresponding derivatives of 4-aminobutyramide ("Gabamide") by catalytic hydrogenation of the cyano group. | 2 |
This is a division, of application Ser. No. 146,247 filed May 5, 1980, now U.S. Pat. No. 4,339,578.
BACKGROUND OF THE INVENTION
The invention is directed to new bisguanamines and their use in the stabilization of formaldehyde solutions.
There are already known phenylene bisguanamines of the formula ##STR2## (see German AS No. 2,358,856). Besides there are known alkylene bisguanamines of the formula ##STR3## in which n is a number from 1 to 8, see Booth, Chemistry and Industry August 3, 1968, page 1047. The entire disclosure of Booth is hereby incorporated by reference and relied upon.
Aqueous formaldehyde solutions, especially solutions having a formaldehyde content above 30 weight percent are unstable if the temperatures at which they are stored fall below a certain minimum. There occurs turbidity through the formation of formaldehyde oligomers and finally the precipitation of paraformaldehyde. The higher the concentration of formaldehyde and the lower the storage temperature the more unstable are the solutions. Accordingly to the data in the monograph, "Formaldehyde" by J. F. Walker, 3rd edition, page 95, a 30 percent formaldehyde solution remains stable for up to about 3 months if it is held at at least 7° C. For a 37 percent solution the required minimum temperature is 35° C., for a 45% solution 55° C. and for a 50% solution 65° C. However, a disadvantage of the use of higher storage temperatures is that formic acid forms to a considerable extent in the formaldehyde solutions. This causes corrosion and is particularly disturbing in the use of formaldehyde solutions for condensation reactions.
The above mentioned values refer to formaldehyde solutions which contain less than 1 weight percent methanol as a stabilizer. To be sure by using higher methanol concentrations there can be produced equal storability at lower temperature, but there are required disproportionately high methanol concentrations. For example there is needed in a 37 percent formaldehyde solution for a storage temperature of 21° C., a methanol content of 7%, for 7° C. a methanol content of 10% and for 6° C. a methanol content of 12%. The addition of methanol, however considerably increases the cost of the formaldehyde solutions, especially since the methanol is generally lost in using the solutions. Apart therefrom through the methanol the speed of reaction in numerous condensation reactions, for example in the condensation with melamine, is reduced.
Besides methanol there are known as stabilizers (for formaldehyde), ethanol, propanol-1, propanol-2, ethylene glycol, glycerine, urea, methyl urea, dimethyl urea, thiourea, diethyl thiourea, formamide, melamine, methylol melamine and acetoxime (J. F. Walker, Formaldehyde", third edition, page 95, U.S. Pat. No. 2,000,152 , U.S. Pat. 2,002,243 and Swain U.S. Pat. No. 2,237,092). However, these materials must be used in concentrations of at least 2% to be effective.
Stabilizing agents which can be used in lower concentrations are for example ether, acetals of polyhydric alcohols such as pentaerythritol, sorbitol and polyethylene glycol, esters of these polyhydric alcohols and higher fatty acids, higher alcohols such as heptanol, octanol, decanol, hydroquinone, polyvinyl alcohol, its esters and acetals (Halpern U.S. Pat. No. 3,183,271; British patent 1,129,507 Japanese Pat. No. 30-3396. However, a disadvantage is that the activity of these materials is insufficient at lower concentrations and temperatures.
Furthermore, it is known to add as stabilizers lipophilic colloids such as polyoxyethylene lauryl ether (HLB (hydrophilic, lipophilic balance)-value=9.5), lipophilic sorbital esters of higher fatty acids such as sorbitol monolaurate (HLB value=8.6) or soluble or partially soluble hydrophilic colloids such as methyl cellulose, hydroxypropyl methyl cellulose, ethyl cellulose, gelatin, pectin and cellulose acetostearate. They are used in concentrations below 0.1% or below 0.5% (German OS 1443566, Prinz U.S. Pat. No. 3,137,736). Also in these cases the stabilizing action in formaldehyde solutions having a methanol content below 1% at low temperatures is not sufficient.
There also have been used as stabilizers 2,4-diaminotriazine (1,3,5) or its methylol derivatives which contain in the 6-position an aliphatic residue having 7 to 9 carbon atoms or an alkoxy or an alkylmercapto group having 5 to 10 carbon atoms (Bornmann German Pat. No. 1205073 and Belgian Pat. No. 719245). Bornmann shows that alkyl guanamines having an alkyl chain length of below 7 carbon atoms or above 9 carbon atoms are poorer stabilizers than those with 7 to 9 carbon atoms. The stabilizer effect goes down even further as the alkyl group increases from 11 to 15 carbon atoms. For a good stabilizing effect the concentration of the added aminotriazine must be 0.05 to 0.2%.
There have also been employed for stabilizing formaldehyde solutions, mixtures of guanamines, for example butyroguanamine, benzoguanamine, acetoguanamine and their methylol derivatices with fatty acid esters, ethers or acetals of a polyhydric alcohol, hydroquinone, polyvinyl alcohol as well as esters or acetals of polyvinyl alcohol. In these mixtures the guanamine must be used in concentrations of 0.08%, especially of 0.1% if a sufficient activity is to be attained (Matsuora, German AS 1219464).
Besides it is known to use as stabilizers methoxymethyl, ethoxymethyl, propoxymethyl and butoxymethyl derivatives of aceto-, propio-, butyro- and benzoguanamines which are mixed with reaction products of formaldehyde with ethylene glycol, propylene glycol, polyethylene glycol, polypropylene glycol, glycerine, trimethylolpropane, pentaerythritol, sorbitol or polyvinyl alcohol and with aceto-, propio-, butryo- or benzoguanamine or with methyl-, ethyl-, propyl-, butyl-, cyclohexyl-, benzyl- or phenyl melamine (Ishizuka German AS 12268608). The concentrations in which the various guanamines or their mixtures are employed lie between 0.0025 and 0.06%. However, at these low stabilizers concentrations an elevated storage temperature is required if there is to be produced a sufficient stability of the formaldehyde solutions. If higher concentrations, namely 0.001 to 0.1% of the guanamine are used with 0.1 to 1.0% of melamine (Dakli German Pat. No. 1768915) it is true that the stabilization is better but the reactibility of the formaldehyde for condensation is reduced considerably.
It is also known that the activity of the guanamines or their methylol derivatives can be increased if there are additionally used hydrophilic polyglycol ethers of fatty alcohols or of partial esters of polyhydric alchols with fatty acids or ion-active surface active substances such as phosphoric acid esters of nonylphenyl polyethylene glycols. However, also in these cases the activity is still not satisfactory.
Finally there is also known the employing of phenylene bisguanamine as stabilizer (Diem, German As No. 2358856). This material it is true shows a better activity, however, it is relatively difficulty accessible and particularly exhibits the disadvantage that it is very difficultly soluble. Therefore it is difficult and requires much time to bring the necessary amount of stabilizer into soluble form. The alkylene bisguanamines (II) are to be sure considerably easier to dissolve, but they have either no stabilizing effect or only very small stabilizing effect.
SUMMARY OF THE INVENTION
There have now been found alkylene bisguanamines of the formula ##STR4## where n is a number from 10 to 20. Thus n can be 10, 11, 12, 14, 16, 18 or 20 for example.
The alkylene bisguanamines of the invention can be produced in the same way as the known alkylene bisguanamines (II), for example by reaction of the corresponding aliphatic dinitrile with dicyandiamide in a polar solvent such as dimethyl sulfoxide, corresponding to the process in Booth, Chemistry and Industry 1968, page 1047.
For example for the production of dodecanobisguanamine there is employed 1,10-dicyanodecane, for the production of hexadecanobisguanamine there is employed 1,14-dicyanotetradecane, for the production of octadecanobisguanamine there is employed 1,16-dicyanohexadecane, for the production of eicosanobisguanamine there is employed 1,18-dicyanooctadecane and for the production of decanobisguanamine there is employed 1,8-dicyanooctane.
Furthermore there has now been found a process for the stabilization of formaldehyde solutions, those having a methanol content of less than 1% being preferred, using bisguanamines as stabilizers wherein there are employed as stabilizers the alkylene bisguanamines (III) of the invention. While the known alkylene bisguanamines (II) are unsuited for this purpose, the compounds (III) of the invention act produce outstanding stabilization. In contrast to phenylene bisguanamine (I) they have the particular advantage that they are considerably more readily soluble and therefore much easier to use.
According to the invention there are preferably employed as stabilizers the alkylene bisguanamines of formula III in which n is a number from 10 to 16, especially a number from 14 to 16.
The amount of the stabilizer to add to the formaldehyde solution depends in a given case to a certain degree on the formaldehyde content and the storage temperature of the solutions. In most cases there is employed a stabilizer content between 0.001 and 0.5 weight percent. Preferably there are chosen stabilizer contents between 0.005 and 0.10, particularly between 0.01 and 0.03 weight percent.
Unless otherwise indicated all parts and percentages are by weight.
The process can comprise, consist essentially of or consists of the steps set forth and the compositions can comprise, consist essentially of or consist of the materials set forth.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
(a) Production of the Alkylene Bisguanamine
EXAMPLE 1
There were dissolved in 500 ml of dimethyl sulfoxide 210 grams (2.5 moles) of dicyandiamide, which hereby was warmed to 60° C. There were introduced into this solution 192 grams (1.0 mole) of 1,10-dicyanodecane and then there were added 30 grams of a 50% aqueous potassium hydroxide solution. The mixture was heated to 135° C., held at this temperature for 45 minutes, then cooled to 100° C. and finally diluted to double its volume through the addition of 500 ml of water. There was separated from the warm mixture the precipitated dodecano-bisguanamine. It was washed with water and recrystallized from dimethyl sulfoxide. The yield was 346 grams, corresponding to 96% based on the 1,10-dicanodecane employed. The dodecanobisguanamine had a melting point of 290° C. The elemented analysis was
______________________________________ C H N______________________________________found 53.0 8.0 38.7calculates asC.sub.16 H.sub.28 N.sub.10 53.3 7.8 38.9______________________________________
The dodecanobisguanamine was identified by IR and NMR spectroscopically and also mass spectrographically.
EXAMPLE 2
The procesure was the same as in Example 1 but there was reacted 1,11-dicyanoundecane to form tridecanobisguanamine. Melting point of the guanamine: 219° C. Elemental analysis:
______________________________________ C H N______________________________________found 55.0 7.6 37.3calculated asC.sub.17 H.sub.30 N.sub.10 54.5 8.0 37.5______________________________________
EXAMPLE 3
The procedure was the same as in Example 1 but there was reacted 1,12-dicanododecane to form tetradecanobisguanamine. Melting point of the guanamine: 180° C. Elemental analysis:
______________________________________ C H N______________________________________found 56.7 8.5 34.5calculated asC.sub.18 H.sub.32 N.sub.10 56.8 8.5 35.7______________________________________
EXAMPLE 4
The procedure was the same as in Example 1 but there was reacted 1,4-dicyanotetradecane to form hexadecanobisquanamine. Melting point of the guanamine: 219° C.
Elemental analysis:
______________________________________ C H N______________________________________found 58.5 8.5 32.8calculated asC.sub.20 H.sub.36 N.sub.10 57.7 8.7 33.6______________________________________
EXAMPLE 5
The procedure was the same as in Example 1 but there was reacted 1,16-dicyanohexadecane to form octadecanobisguanamine. Melting point of the quanamine: 230° C. Elemental analysis:
______________________________________ C H N______________________________________found 59.2 9.1 31.7calculated asC.sub.22 H.sub.40 N.sub.10 59.4 9.1 31.5______________________________________
(B) Stabilization of the Formaldehyde Solutions
There were used formaldehyde solutions with differing contents of formaldehyde and methanol. To these solutions there were added different amounts of bisguanamines as stabilizers and there was examined how long these solutions were stable at a specific storage temperature.
To dissolve the stabilizers in the formaldehyde solutions these were held in each case at 50° C. with stirring for 20 to 30 minutes.
The results are collected in the following tables. The stabilizers, the bisguanamines, are designated by n, the number of methylene groups according to formula III. The stabilizer contents are given in weight percents based on the total formaldehyde solution. As storability there was considered the time in which the solution was stable. The solutions were regarded as stable until there occurred the first separation just detectable by the eye.
TABLE 1______________________________________Solutions containing 37 weight percent formaldehydeand 0.30 weight percent methanol; pH 4.2.Stabilizer Storage StorabilityNr. Type n Content % Temp. °C. Days______________________________________1 10 0.020 0 202 10 0.030 0 >1203 11 0.020 0 304 12 0.020 0 >905 12 0.030 0 >1206 14 0.010 0 >1207 16 0.005 0 108 16 0.010 0 >120______________________________________
TABLE 2______________________________________Solutions containing 40 weight percent formaldehydeand 0.40 weight percent methanol; pH 4.1Stabilizer Storage StorabilityNr Type n Content % Temp. °C. Days______________________________________ 9 10 0.020 10 7010 10 0.030 10 >12011 11 0.020 10 >12012 12 0.020 10 >12013 12 0.010 0 514 14 0.010 10 >12015 16 0.010 0 716 16 0.010 10 >120______________________________________
TABLE 3______________________________________Solutions containing 44 weight percent formaldehydeand 0.45 weight percent methanol; pH 3.9.Stabilizer Storage StorabilityNr Type n Content % Temp. °C. Days______________________________________17 10 0.010 25 218 10 0.015 25 >6019 11 0.015 25 >6020 12 0.010 25 1921 12 0.015 25 >6022 14 0.010 25 >6022 16 0.010 25 >60______________________________________
The entire disclosure of German Priorty application No. P 2919496.5 is hereby incorporated by reference. | There are described new bisguanamines of the formula ##STR1## where n is a number from 10 to 20 and their production. The bisguanamines are stabilizers for formaldehyde solutions and have outstanding qualifications and action for this purpose. | 2 |
CROSS-REFERENCE TO RELATED APPLICATION
This application is a Continuation-in-Part of non-provisional U.S. application Ser. No. 10/034,727 filed Dec. 26, 2001. This application claims priority to non-provisional U.S. application Ser. No. 10/032,727 and U.S. Provisional Application No. 60/300,025, filed Jun. 21, 2001, now abandoned both of which are incorporated herein by reference in their entirety.
BACKGROUND OF THE INVENTION
A longstanding objective within the materials, engineering, biomedical and analytical sciences has been the design of ever-smaller structures and devices for use in miniature systems capable of performing specific functions, such, as sensors, transducers, signal processors or computers. Of particular interest as potential building blocks in this context have been functional materials having predetermined properties. Patterned films composed of suitable polymers and polymer-microparticle composites offer particularly attractive opportunities to realize hierarchically organized structures of functional materials and to provide confinement and segregation for performing “local” chemical reactions.
Several methods of preparing patterned polymer films and polymer-microparticle composites have been described. In one example, polymer molding has been used to prepare polymeric films. Beginning with a master that is fabricated from a silicon (Si) wafer using conventional lithographic techniques, a mold is made using an elastomer such as polydimethylsiloxane (PDMS). The mold is then used to produce replicas in a UV-curable polymer such as polyurethane. The applicability of this technique of polymer molding, long used for replication of micron-sized structures in devices such as diffraction gratings, compact disks, etc., recently has been extended to nanoscale replication (Xia, Y. et al., Adv. Mater. 9: 147 (1997), Jackman, R. J. et al., Langmuir. 15:2973 (1999), Kim, E. et al. Nature 376, 581 (1999).
Photolithography has been used to produce patterned, stimuli-sensitive polymeric films which can be further functionalized with bioactive molecules and which undergo abrupt changes in volume in response to changes in pH and temperature (Chen, G. et al., Langmuir. 14:6610 (1998); Ito, Y. et al., Langmuir 13: 2756 (1997)). UV-induced patterned polymerization of various hydrogel structures within microchannels has been described as a means for the autonomous control of local flow (Beebe, D. J. et al., Nature. 404:588 (2000)).
Surface-initiated ring-opening metathesis polymerization following microcontact printing has been used to create patterned polymer layers which remain attached to the surface and produce structures of controlled vertical and lateral dimensions (Jeon, N. L. et al., Appl. Phys. Lett. 75:4201 (1999)). Other techniques such as thermal radical polymerization (Liang, L., J. Appl. Polym. Sci. 72:1, (1999)) and UV-induced polymerization (Liang, L., J. Membr. Sci. 162:235 (1999)) have been used to generate surface-confined, thin, uniform and stimuli-sensitive polymeric films.
Sarasola, J. M. et al. (J. Electroanal. Chem. 256:433, (1988)) and Otero, T. F. et al. (J. Electroanal. Chem. 304:153, (1991)) describe electropolymerization of acrylamide gels using a Faradaic process. Acrylamide gels are prepared on electrode surfaces by an anodic oxidative polymerization process using the electroactive nature of acrylamide monomers.
Polymerization of crosslinked acrylamide has been reported to produce a matrix of glass-immobilized polyacrylamide pads which were activated with receptor molecules of interest including oligonucleotides or proteins. The use of the resulting porous and highly hydrated matrix for simultaneous monitoring of ligand-receptor binding reactions has been reported (Proudnikov, D. et al., Anal. Biochem. 259:34 (1998); Yershov, G., Proc. Natl. Acad. Sci. U.S.A. 93:4913 (1996), LaForge, S. K., Am. J. Med. Genet. 96:604 (2000); Khrapko, K. R. et al. U.S. Pat. No. 5,552,270, 1996; Ershov,G. M. et al. U.S. Pat. No. 5,770,721, 1998; Mirzabekov et al. U.S. Pat. No. 6,143,499). It should be noted, however, that a potential drawback of the methodology used in these studies is that forming the gel-matrix for the assay is labor-intensive and difficult, especially if a densely packed matrix is desired. Additionally, when the gel-pads of the matrix have sizes on the length scale of microns, it is a considerable technological challenge to deliver the bioactive molecules reproducibly and reliably to each gel-pad in the array.
A process for the assembly of a 3-D array of particles has been reported which is based on the synthesis of a core-shell latex particle containing a core polymer with a glass transition temperature significantly higher than that of the shell polymer. In accordance with that process, particles were assembled into a 3-D close packed structure and annealed in such a way that the core particle remained unaltered while the shell polymer flowed, resulting in a continuous matrix embedding an organized 3-D array of core particles (Kalining, O. and Kumacheva, E., Macromolecules. 32:4122 (1999); Kumacheva, E. et al., Adv. Mater. 11:231 (1999), Kumacheva, E. et al., U.S. Pat. No. 5,592,131 (1999)). However, the reported assembly of the 3D array is quite slow because it relies on particle sedimentation. Second, because the outer shells of the particles are destroyed as a result of annealing, the particles cannot be reused.
The encapsulation of a colloidal crystalline array within a thin, environmentally sensitive hydrogel matrix capable of swelling in response to changes in pH and temperature has also been reported. In other instances, the hydrogel contained immobilized moieties capable of triggering the swelling of the gel in the presence of particular analytes. The swelling of the gel matrix increases the periodicity of the colloidal crystal array and produces a shift in Bragg diffraction peaks in the spectra of the scattered light (Holtz, J. H. et al., Anal. Chem. 70:780 (1998); Hacke, G. et al., U.S. Pat. No. 5,266,238, 1993; Asher, S. A., U.S. Pat. No. 5,281,370, 1994). In most of these references, the process of forming a colloid crystal relies on passive diffusive transport of particles within the prepolymer reactive mixture, which tends to be slow. In one reference, however, a process was reported in which an electric field was applied to a colloid suspension to increase the rate of formation of a colloid crystal. It should be noted that, regardless of whether an electric field is used, the processes reported in these references only produce a simple colloid crystal. More sophisticated colloid crystal structures, such as patterned two-dimensional colloid crystals, are not readily produced by these methods.
Each of the aforementioned references are incorporated herein by reference in its entirety
SUMMARY OF THE INVENTION
One aspect of this invention is to provide a method of forming a patterned polymeric film. In this method, a first electrode is positioned in a first plane and a second electrode is positioned in a second plane that is different from the first plane. A polymerization mixture comprising a monomer and an initiator in an electrolyte solution is added to the space between the first and the second electrode. An AC electric field is generated at an interface between the first electrode and the electrolyte solution. Here, the first electrode may be a light-sensitive electrode. If so, the method further comprises the step of illuminating the first electrode with a predetermined light pattern, such that the illumination, in combination with the AC field generated at the interface between the first electrode and the electrolyte solution, results in the formation of a patterned film in a designated area on the first electrode. The designated area is defined by the illumination pattern. Alternately, the first electrode can be an electrode with a surface and an interior. In this case, the surface or interior (or both) is/are modified to produce spatial modulations in certain properties of the first electrode, particularly properties that affect the local distribution of the electric field at the interface between the electrode and the electrolyte solution. As a result, the generation of an AC electric field at the interface results in the formation of the patterned film in a designated area of the first electrode. In this second case, the designated area is defined by spatial modulations in the properties of the first electrode.
Another aspect of this invention is to provide a method of forming an assembly of particles embedded in a polymeric film. In this method, a first electrode and a second electrode are provided. A polymerization mixture comprising a monomer and an initiator in an electrolyte solution also containing a plurality of suspended particles is added to the region between the first and the second electrode. An AC electric field is generated at an interface between the first electrode and the electrolyte solution. When the first electrode is a light-sensitive electrode, the method further comprises the step of illuminating the first electrode with a predetermined light pattern, such that the illumination, in combination with the AC field generated at the interface between the first electrode and the electrolyte solution, results in the formation of an assembly of particles in a designated area corresponding to the predetermined light pattern on the first electrode. The designated area is defined by the illumination pattern. Alternately, the first electrode can be an electrode with a surface and an interior. In this case, the surface or interior (or both) is/are modified to produce spatial modulations in certain properties of the first electrode, particularly properties that affect the local distribution of the electric field at the interface between the electrode and the electrolyte solution. As a result, the generation of an AC electric field at the interface results in the formation of the assembly of particles in a designated area of the first electrode. In this second case, the designated area is defined by spatial modulations in the properties of the first electrode. After the particle assemblies are formed, the polymerization mixture is polymerized to form a polymer-particle composite, which has an assembly of particles embedded in the polymer.
In another aspect of this invention, a method of detecting a binding interaction between a biomolecule and a target compound is provided. This method comprises providing an assembly of beads embedded in a hydrophilic polymeric matrix. The beads have biomolecules attached to their surfaces. Subpopulations of beads are provided, wherein each bead of a given subpopulation can be distinguished by the type of biomolecule attached to it, as well as by a unique chemical or physical characteristic that identifies the bead type. The beads are placed in contact with a target compound so as to allow a target compound to bind to the corresponding biomolecule to form a target-biomolecule complex. The target-biomolecule complex is then detected. The biomolecule of the target-biomolecule complex is then identified by means of the unique chemical or physical characteristic of the type of bead associated with the complex.
Yet another aspect of this invention is to provide a method of forming an assembly of particles embedded in a gel. This method comprises the step of providing a first electrode and a second electrode. An electrolyte solution containing a gellable component and a plurality of suspended particles is added to the region between the first and second electrode. The formation of gels by suitable gellable components is preferably temperature dependent. An AC electric field is generated at an interface between the first electrode and the electrolyte solution. When the first electrode is a light-sensitive electrode, the method further comprises the step of illuminating the first electrode with a predetermined light pattern, such that the illumination, in combination with the AC field generated at the interface, results in the formation of an assembly of particles in a designated area of the first electrode. The designated area in this case is defined by the illumination pattern. Alternately, the first electrode can be an electrode having a surface and an interior. In this case, the surface and/or interior of the electrode is/are modified to produce spatial modulations in certain properties of the first electrode, particularly properties affecting the local distribution of the electric field at the interface. Generation of an AC electric field at the interface results in the formation of an assembly of particles in a designated area of the first electrode. The designated area is defined by the spatial modulations in the properties of the first electrode. After an assembly of particles is formed, the temperature of the gellable component is decreased while maintaining the AC field, in order to form a polymer-particle composite gel. The composite gel obtained in this way comprises an assembly of particles embedded in a gel.
This invention also provides a polymer-bead composite. The composite comprises a assembly of beads embedded in a hydrophilic polymeric matrix. The beads have biomolecules attached to their surfaces, and each type of bead can be distinguished by the biomolecules attached to it. Each type of bead is further distinguishable by a unique chemical or physical characteristics that identifies the bead type.
Another aspect of this invention is to provide a method of sorting one population of particles from another. This method involves providing a cell that comprises a first electrode positioned in a first plane and a second electrode positioned in a second plane different from the first plane. A polymerization mixture containing a monomer and an initiator in an electrolyte solution is added to the region between the first and the second electrode. The electrolyte solution also contains a plurality of particles suspended in the solution. The particles comprise a mixture of at least two populations of particles having different relaxation frequencies. An AC electric field is applied to an interface between the first electrode and the electrolyte solution. The frequency of the AC field is selected such that an array composed of particles having relaxation frequencies exceeding the frequency of the applied field are selectively assembled. The particles having relaxation frequencies less than said applied frequency are not assembled. When the first electrode of this method is a light-sensitive electrode, the method further comprises the step of illuminating the first electrode with a predetermined light pattern, such that the illumination, in combination with the AC field generated at the interface, results in the formation of an assembly of particles in a designated area of the first electrode. The designated area in this case is defined by the illumination pattern. Alternately, the first electrode may be an electrode having a surface and an interior. In this case, the surface and/or interior of the electrode is/are modified to produce spatial modulations in certain properties of the first electrode, particularly properties affecting the local distribution of the electric field at the interface. Generation of an AC electric field at the interface results in the formation of an assembly of particles in a designated area of the first electrode. The designated area is defined by the spatial modulations in the properties of the first electrode. After the assembly of particles is formed, the polymerization mixture is polymerized to form a polymer-particle composite. The composite formed in this manner comprises an array of particles embedded in the polymer. Particles that are not assembled in the array are removed from the cell, either before or after the polymerization step.
Yet another aspect of this invention is to provide a method of sorting one population of particles from another. This method comprises the step of: providing a first electrode positioned in a first plane and a second electrode positioned in a second plane different from the first plane. An electrolyte solution containing a gellable component and a plurality of suspended particles is added to the region between the two electrodes. The formation of gels by gellable components suitable for this invention is either temperature dependent or activated by light. The plurality of particles comprises a mixture of at least two populations of particles having different relaxation frequencies. An AC electric field is applied at an interface between the first electrode and said electrolyte solution. The frequency of the AC field is selected such that an array composed of particles having relaxation frequencies exceeding the frequency of the applied field is selectively assembled. Particles having relaxation frequencies less than the applied frequency are not assembled. When the first electrode is a light-sensitive electrode, the method further comprises the step of illuminating the first electrode with a predetermined light pattern, such that the illumination, in combination with the AC field generated at the interface, results in the formation of an assembly of particles in a designated area of the first electrode. The designated area in this case is defined by the illumination pattern. Alternately, the first electrode is an electrode having a surface and an interior. In this case, the surface or interior of the electrode is modified to produce spatial modulations in certain properties of the first electrode, particularly properties affecting the local distribution of the electric field at the interface. Generation of an AC electric field at the interface results in the formation of an assembly of particles in a designated area of the first electrode. The designated area is defined by the spatial modulations in the properties of the first electrode. After a particle array is formed, particles that are not part of the array are removed. The gel is then formed. If temperature dependent gellable components are used, the temperature of the gellable component is decreased while maintaining the AC field to form a polymer-particle composite gel. Alternately, if photoactivated gellable components are used, the composite gel can be formed by irradiation with light. The composite gel formed by this method comprises an assembly of particles embedded in gel.
Yet another aspect of this invention is to provide a method of producing an organized assembly by transforming a homogeneous fluid mixture or suspension comprising a gellable component and a plurality of particles within a reactor, into one or more heterogeneous assemblies. The method comprises the following steps: (a) actively forming a spatial arrangement of a plurality of particles in designated regions of one or more bounding surfaces of the reactor. Here, the active formation is mediated by an external field and sustained in the arrangement after the formation by the field; (b) forming a gel in the presence of the external field, in order to form a gel-particle composite. In another aspect of this invention, a method of performing an assay is provided. This method comprises the step of providing a first electrode and a second electrode. A polymerization mixture comprising a monomer and an initiator in an electrolyte solution also containing a plurality of suspended particles is added to the region between the first and the second electrode. The particles comprise subpopulations of particles, with each subpopulation being distinguishable by the type of binding agent attached to the surface. The particles also have a chemically or physically distinguishable characteristic. An AC electric field is generated at an interface between the first electrode and the electrolyte solution. When the first electrode is a light-sensitive electrode, the method further comprises the step of illuminating the first electrode with a predetermined light pattern, such that the illumination, in combination with the AC field generated at the interface between the first electrode and the electrolyte solution, results in the formation of an assembly of particles in a designated area corresponding to the predetermined light pattern on the first electrode. The designated area is defined by the illumination pattern. Alternately, the first electrode can be an electrode with a surface and an interior. In this case, the surface or interior (or both) is/are modified to produce spatial modulations in certain properties of the first electrode, particularly properties that affect the local distribution of the electric field at the interface between the electrode and the electrolyte solution. As a result, the generation of an AC electric field at the interface results in the formation of the assembly of particles in a designated area of the first electrode. In this second case, the designated area is defined by spatial modulations in the properties of the first electrode. After the particle assemblies are formed, the polymerization mixture is polymerized to form a polymer-particle composite, which has an assembly of particles embedded in the polymer. In some embodiments of this invention, at least one electrode is then removed to expose the particles embedded in the polymer. The exposed particles are placed in contact with a solution containing at least one target analyte and the binding reaction between the binding agent and the target analyte is detected. In other embodiments of this invention, the polymer-particle composite is exposed to a target analyte while it is still sandwiched between the two electrodes.
The present invention provides methods for synthesizing patterned polymeric films and polymer-microparticle composites. The methods are simple to implement and flexible because they are compatible with a variety of polymer chemistries. Also provided is an apparatus useful for making the patterned polymer films and polymer-microparticle composites. Patterned polymer films and polymer-microparticle composites and their uses are also provided.
BRIEF DESCRIPTION OF DRAWINGS
FIG. 1 is an illustration showing an experimental configuration for LEAPS. FIG. 2 a contains a photograph showing a patterned gel film and a second photograph showing a close-up of a section of the film.
FIG. 2 b is a photograph showing a free-standing gel film imaged in aqueous phase.
FIG. 3 a contains a photograph showing a patterned gel-microparticle composite created via thermal initiation and a close-up of the central section of the composite.
FIG. 3 b is a photograph showing a monolithic gel-microparticle composite created via UV-initiation.
FIG. 4 a is an illustration showing a flipped gel-particle composite.
FIG. 4 b is an illustration showing a flipped gel-particle composite with the particles partially exposed.
FIG. 5 is an illustration showing a cleaved gel-particle composite.
FIG. 6 is an illustration showing two exemplary processes for produce porous a gel-particle composite.
FIG. 7 is an illustration showing a process to produce a gel-particle composite by reversible gelation.
FIG. 8 is an illustration showing a process to produce inorganic-organic hybrid films.
FIG. 9 is an illustration showing a process to produce and to characterize a magnetic gel-particle composite.
FIG. 10 is an illustration showing a DNA hybridization assay using a flipped polymer-gel composite. The set of four images obtained from analyzing the gel in different color channels were then analyzed to determined the results of the assay, as depicted in the bar graphs in FIG. 10 .
FIG. 11 is an illustration showing electrophoretically assisted DNA hybridization.
FIG. 12 is an illustration showing an immunoassay using a flipped polymer-gel composite. The set of four images obtained from analyzing the gel in different color channels were then analyzed to determine the results of the assay, as depicted in the bar graphs in FIG. 12 .
FIG. 13 is an illustration showing the analysis of multiple samples on a monolithic gel chip.
FIG. 14 is an illustration showing a process to implement a cell-bead heteroreactor.
FIG. 15 is an illustration showing a heteroparticle arrays.
FIG. 16 is an illustration showing a glucose biosensor.
FIG. 17 is an illustration showing microparticle-encoded vesicles embedded in a gel film.
FIG. 18 is an illustration showing a gel-embedded cellular array and its use.
FIG. 19 shows the effect of gel chemistry and formation conditions on diffusion.
FIG. 20 a is a photograph showing the close up of a microparticle array in a gel-microparticle composite film created by using agarose as the gel matrix and 2.8 micron Oligo(dT) 25 particles. The thickness of the film was ˜100 microns.
FIG. 20 b is an illustration showing the results of a hybridization assay using the 2.8 micron Oligo(dT) 25 particles. The target was a fluorescently labeled 100 bp synthetic DNA fragment with a complementary poly(A) tail. The thickness of the film was approximately 100 microns.
FIG. 20 c is an illustration showing the results of an enzymatic extension based hybridization assay using a gel-microparticle composite film consisting of two populations of particles: one with a matching (positive) oligonucleotide probe and the other with a nonmatching (negative) oligonucleotide probe. The target was a fluorescently labeled PCR amplified ˜280 base pair fragment. The thickness of the film was about 50 microns.
DETAILED DESCRIPTION OF THE INVENTION
Patterned polymeric films and polymer-microparticle composites are useful in many areas of technology, including biology, electronics, optoelectronics, and materials science. This invention provides methods for manufacturing such patterned films and polymer-microparticle composites, as well as the pattern films and composites themselves. One advantage of this invention is that it provides a rapid method of forming an ordered polymer-microparticle composite that is suitable for use in biological assays. Another advantage is that the formation of the polymer-microparticle composites is even reversible under certain conditions, such that the composite can be disassembled at will to recover the microparticles after a biological assay is completed. Further, in contrast to gel array based assays reported earlier, the methods of forming the polymer-microparticle composites of this invention are very simple, which make the composites attractive for large-scale, multiplexed assays.
Certain embodiments of this invention make use of the methods collectively known as “LEAPS” (“Light-Controlled Electrokinetic Assembly of Particles near Surfaces” as described in U.S. Pat. No. 6,251,691, hereby incorporated by reference). In these embodiments, LEAPS is used to direct the self-assembly of microparticles to form arrays in designated positions on a planar or substantially planar substrate. In using LEAPS in accordance with the methods, of this invention, it is possible to form one or more microparticle arrays on a substrate. When a plurality of microparticle arrays is desired, the arrays may be formed simultaneously or sequentially on the substrate. Sequential formation of a plurality of arrays is possible because LEAPS can be used to spatially confine microparticle arrays that are already formed. The use of LEAPS in combination with externally triggered, template-directed gel chemistries provides heterostructures that are organized in accordance with user-defined architecture designed to meet the requirements associated with the execution of specific functions. Applications of the process to the fabrication of functional materials, sensors and more generally chemical transducers and information processors also are of interest.
Formation of Patterned Polymeric Film
The present invention provides methods for forming patterned polymeric film using LEAPS. In certain embodiments of this invention, a polymerization mixture is provided comprising a monomer and an initiator in an electrolyte solution. Preferably, the polymerization mixture also contains a cross-linker, with the monomer, initiator and the crosslinker dissolved in the electrolyte solution. When LEAPS is used to pattern the polymeric films, this mixture is placed between a first electrode (e.g., silicon), which may be light sensitive and/or patterned and a second electrode (e.g., indium-tin-oxide (ITO)) that is parallel to the first. An AC electric field is generated at the interface between the electrolyte solution and the first electrode. Lateral impedance gradients at the interface, set up by the patterning or illumination, give rise to local recirculating electro-osmotic fluid motion, which effectively transports fluid (and particles if they are present) from regions of high impedance to regions of low impedance. Depending on the initiators used, the application of the AC electric field, in addition to the illumination of the first (when a light-sensitive electrode is used) or the patterning of the electrode (when a patterned electrode is used), induces formation of a patterned polymeric film on the low impedance regions of the electrode.
In preferred embodiments, the polymerization is triggered at a desired time by using initiators that are heat or photoactivated. Such heat or photoactivated triggering occurs when heat-generated or UV-generated free radicals diffuse and react with monomers to produce initially oligomers and finally a crosslinked polymer film.
As the gel film grows, a moving reaction extends into the solution with time. In case of the heat-induced polymerization, polymerization starts from the first electrode. Due to the presence of LEAPS-mediated, strong convective transport near the first electrode surface, the polymerization process is triggered preferentially in the low impedance areas on the first electrode, thereby giving rise to a spatially patterned polymeric film on said electrode. In case of UV-induced polymerization, however, polymerization starts at the second electrode and produces an unpatterned monolithic gel.
Gels of the present invention may have a wide range of porosity and include non-porous, microporous and macroporous gels. It is to be understood that non-porous gels refer to gels with a microscopic structure such that the space between the macromolecular chains is the main area for diffusion. Generally, non-porous gels do not have a network of pores and any pores that are present have a pore size less than 5 nm. It is to be understood that microporous gels refer to gels which have a porous structure with pore sizes ranging from about 5 to about 50 nm. It is to be understood that macroporous gels refer to gels which have a porous structure with a pore size greater than 50 nm. Furthermore, depending on the polymer components, the degree of porosity and size of “pores” is based on the density of the lattice or matrix formed by the crosslinking of polymer strands.
Non-limiting examples of useful gels are polyacrylamide gels, which can have pore sizes ranging from a few nm to also 15 to 20 nm in highly diluted formulations. To facilitate the penetration of large DNA fragments and other molecules into gels, macroporous polyacrylamides may be prepared by polymerizing in the presence of preformed polymers such as poly(ethylene glycol)(PEG), polyvinyl pyrrolidone (PVP), hydroxymethyl cellulose (HMC) etc. (Righetti, P. G. and Gelfi, C. 1996. J. Chromatogr. B. 699: 63–75). Highly hydrophilic monomers, such as trisacryl may also be used to produce highly porous gels (Gelfi, C., et al. 1992. J. Chromatogr. 608: 333–341). FIG. 6 illustrates the protocol to form a porous gel using preformed polymers.
The present invention, in contrast to several known methods, does not require complex implementation, such as use of a mask, in preparation of patterned gel films. In addition, the methods of the present invention allow increased flexibility in choice of monomers, crosslinkers and initiators used. It should, however, be noted that high viscosity of the polymerization mixture and high ionic concentration may impede with the proper functioning of LEAPS by interfering with the interfacial fluid flow. Accordingly, it is recommended that the ionic concentration of the polymerization mixture be about 1.0 mM or lower, preferably between about 0.01 mM to 0.1 mM. This may be accomplished by selecting initiators to maintain low ionic concentration of the mixture. Initiators, like monomers and crosslinkers, are well known in the art and may readily be obtained from commercial sources.
Two types of initiators are preferably used with this invention, namely thermal initiators and photoinitiators. Non-limiting examples of thermal initiators include VA-044 (2,2′-Azobis (N,N′ dimethyleneisobutyramidine) dihydrochloride, V-50 (2,2′-Azobis(2-amidinopropane) dihydrochloride, VA-061 (2,2′-Azobis (N, N′dimethyleneisobutyramidine), V-501 (4,4′-Azobis (4-cyanopentanoic acid), VA-086 (2,2′Azobis[2-methyl-N-(2-hydroxyethyl) propionamide). Non-limiting examples of photoinitiators include Ciba IRGACURE 2959 (1-[4-(2-Hydroxyethoxy)-phenyl]-2-hydroxy-2-methyl-1-propane-1-one), (Ciba Specialty Chemicals Inc.), DEAP (Diethoxyacetophenone) (Acros Organics), Ciba DAROCUR 1173 (2-Hydroxy-2-methyl-1-phenyl-propan-1-one), (Ciba Specialty Chemicals Inc.), Ciba DAROCUR BP (Banzophenone), (Ciba Specialty Chemicals Inc.). As for the monomers and crosslinkers, it is recommended that low viscosity monomers and crosslinkers be used, such that the viscosity of the polymerization mixture is about 100 cp or less, more preferably 10 cp or less. Examples of monomers useful for this invention include those that are water soluble, with non-limiting examples including acrylamide, ethylene glycol acrylate, hydroxyethylacrylate, and acrylic acid. Other suitable monomers are not water soluble, but are still useful provided that a polarizable liquid medium is also used, as described below. Crosslinkers that are useful for this invention include those that are water soluble. Non-limiting examples include methylene-bis-acrylamide, PEG diacrylates, and ethyleneglycol diacrylate. Crosslinkers that are not water soluble may also be used as well, provided that a polarizable liquid medium is used in conjunction.
When the patterned film to be produced is a hydrogel, water-soluble monomers are preferred. In addition, when said film is optically transparent, the desired monomer concentration may be adjusted according to the type of gel to be produced (e.g., self-supporting or cleaved gel). In one embodiment, a mixture of acrylamide and bisacrylamide of varying monomer concentrations, from about 20% to about 3%. (acrylamide:bisacrylamide=37.5:1, molar ratio) may be used to produce a hydrogel. In preferred embodiments, the polymeric film obtained comprises a cross-linked alkylacrylamide or hydroxyalkylmethacrylate hydrogel.
The AC voltage depends on the polymerization mixture and is readily adjusted until the desired polymeric film (or polymer-microparticle composite) is formed. Preferably, the voltage applied is in the range of about 0.5 to about 15 V p-p (peak-to-peak voltage) and the frequency is preferably more than about 10 Hz and less than about 500 kHz, more preferably about 1 kHz to 10 kHz.
In one embodiment of the invention, LEAPS is carried out in a fluidic microcell formed by sandwiching a spacer between the first and second electrode. LEAPS and polymerization is then conducted as described above. In preferred embodiments of the present invention, an electrolyte solution (more preferably, an aqueous solution) is used in the polymerization mixture, e.g., to dissolve monomers, crosslinkers and initiators. In certain embodiments, other polarizable liquid media may be used, including non-aqueous solutions. In using a non-aqueous solution (e.g., DMSO and acetonitrile), an environment-dependent characteristic frequency of the particles known as the “relaxation” “frequency” is shifted to lower values than what would be observed in an aqueous solution. Among other things, the relaxation frequency of the particles is a measure of the particles' ability to move in response to time-varying electric fields.
The hydrogels of the present invention may be functionalized by a variety of methods known in the art. For example, during the polymerization step itself small amounts of functional monomers may be introduced along with the polymerization mixture (e.g., acrylamide mixture). Acrylic acid, 2-hydroxyethymethacrylate (HEMA), diethylaminoethylmethacrylate hydrochloride etc. may be incorporated into the hydrogel so that the micropatterned gel may be chemically addressed via the carboxy, hydroxy and amino functional groups. Biomolecules of interest may subsequently be immobilized in the gel using suitable chemistry and linker molecules.
Small probe molecules or functional co-monomers may also be introduced into the hydrogel using the same approach to yield novel sensor and stimuli-responsive hydrogel structures that can respond to a variety of inputs such a pH, temperature, electric field, light etc. Microscale structures made from such stimuli-responsive materials may act as an actuator, for example for controlling fluid flow (valve). Such structures are be self-regulating and would not require an external power source.
Polymer-Microparticle Composites
By providing a plurality of particles suspended in the polymerization mixture, the methods for patterned polymeric film synthesis, as described in the preceding section, may be used to obtain an assembly of the particles embedded in a polymeric film (also referred to as a “polymer-microparticle composite” or a “heterostructure”). The term “particle” as used herein includes, but is not limited to, colloidal particles (e.g., silica, modified polystyrene or other polymers), microspheres, eukaryotic and prokaryotic cells, micelles, vesicles (e.g., liposomes) and emulsion droplets. In preferred embodiment, the size of the particles range from about 0.2 to about 20 μm in diameter.
The formation of the polymer-microparticle composite is comprised of two stages. First, particle assemblies (e.g., planar particle assemblies, more preferably particle arrays) are formed from a particle suspension that also contains all of the ingredients required for subsequent in-situ gel formation, as described previously. In these embodiments, LEAPS may be used to form the particle assemblies. Alternately, other methods may be used as well. For example, if magnetic particles are used, a magnetic field may be used to induce particle array formation. The second stage of composite formation comprises the formation of a polymeric film formed to produce the polymer-microparticle composite. In one preferred embodiment, gels are formed by heat-initiated in-situ polymerization to form a composite in which the gels are spatially patterned. In another preferred embodiment, the gels are formed by UV-initiated in-situ polymerization to obtain a composite in which the gels are monolithic (not patterned).
For a given particle size, the voltage and frequency can be selected such that the transport of the fluid and particle is achieved from a high impedance to a low impedance region on the chip. By way of example, for a particle size of 2 microns, a voltage of from about 0.5 to about 20 V (AC peak-to-peak) and a frequency of from about 100 Hz to about 3 kHz can be applied to achieve particle/fluid transport. For a particle size of 5 microns, a voltage of from about 0.5 to about 20 V (AC peak-to-peak) and a frequency from about 100 Hz to about 1 kHz can be applied. For a particle size of 10 microns, a voltage of from about 0.5 to about 20 V (AC, peak-to-peak) and a frequency of from about 50 Hz to about 200 Hz can be applied. Fluid and particle transport and assembly may be monitored by video microscopy permitting frame capture and digitization of frames for further analysis.
The thermal free radical polymerization may be initiated by heating the polymerization mixture (e.g., by heating the LEAPS cell), for example, to about 40 to 45° C., for about 1 to 10 minutes, using an IR lamp, while maintaining the AC electric field at the electrolyte solution-electrode interface, to form a patterned film or polymer-microparticle composite.
The polymerization may also be triggered by irradiating the polymerization mixture with UV-light. For example, in the presence of the applied AC electric field, polymerization may be triggered by using a mercury lamp source. A wide range of wavelengths, spanning from about 250 to 340 nm, may be used, with exposure times ranging from about 15 seconds to about 10 minutes. In one preferred embodiment, the concentration of monomers in the polymerization mixture is about 10% by weight, and 2-hydroxy-4′-hydroxyethoxy-2-methylpropiophenone) may be used as the initiator to give a 1.5% by weight solution.
In certain embodiments, colloidal particles which are anionic or cationic particles ranging from about 0.5 μm to about 15 μm in diameter are used. In certain preferred embodiments, these particles are functionalized by attaching a variety of chemical functional groups to their surfaces. The process of forming composite gel-particle films may be readily extended to particles that display biomolecules attached on their surfaces, such as receptors or ligands. In certain embodiments, oligopeptides, proteins, oligonucleotides or nucleic acid fragments may also be attached to the particle surfaces. The particles may also be encoded by use of a chemically or physically distinguishable characteristic that uniquely identifies the biomolecules attached to those particles, an example of which includes color encoding the particles using fluorophore or chromophore dyes. Such a process allows chemical immobilization of functionalized microparticle assemblies or arrays for a variety of biochemical assays, including binding and functional assays. Examples 6 to 9 describe a number of these assays.
LEAPS also enables the co-assembly of a binary mixture of smaller beads along with larger assay beads in designated areas of the substrate ( FIG. 15 ). Once arranged in an array format, the smaller beads undergo two-dimensional crosslinking due to electrostatic interactions or reactions between chemical moieties on the surfaces of neighboring beads. The two-dimensional crosslinked aggregate created in this process acts as an inert mold for the larger assay beads and thereby immobilizes them. The advantages of the protocol include the ease of implementation, control of spatial localization and good immobilization efficiency.
In certain embodiments, the particles used in preparing polymer-microparticle composites may be magnetic. In certain other embodiments, examples of the particles used are eukaryotic or prokaryotic cells, or liposomes. The polymer-microparticle composites produced using these particles may also be used in various biochemical assays, including the assays described in the Examples.
The particles useful in the preparation of the composite may also comprise inorganic particles, including metal particles, semiconductor particles and glass particles. The inorganic particles may also be coated with a polymeric shell.
Fabrication of a Gel-Embedded Planar Array of Vesicles
There is a growing interest in developing miniaturized sensing, sampling and signal amplifying structures coupled with an analytical measuring element to carry out a variety of bioassays. The sensing component typically reacts or interacts with an analyte of interest to produce a response that can be quantified by an electrical or optical transducer. The most common configuration uses immobilized biomolecules on solid phase supports while another less common approach uses living microorganisms or cells or tissues as the sensing structure.
Unilamellar vesicles are composed of a single lipid bilayer shell that encloses an entrapped aqueous compartment. Methods have been described to prepare giant unilamellar vesicles with sizes approaching that of cells. Such vesicles are attractive as ultra-small reaction vessels or “artificial organelles” in which the reaction is confined and separated from an external medium. Vesicles containing reconstituted integral membrane proteins provide a synthetic chemical structure to study the function of such proteins, including many cell surface receptors. In addition, the surface of such vesicles can be decorated with a variety of receptor moieties that mimic a natural cell, thereby allowing complex biochemical reactions and/or interactions to be studied (Lasic, D. D. Ed. “Liposomes: From Physics to Applications”, 1 st ed., Elsevier Science B.V.: Amsterdam, 1993.)
Given a mixture of two types of vesicles, each containing one of the reactants of a reaction of type A+B→C, two vesicles of different type may be brought into close proximity, (e.g., by forming a close-packed planar array). By applying a pulsed electric field in accordance with methods known in the art, the vesicles are fused to form a larger vesicle in which the reaction A+B→C can now occur. In a preferred embodiment, “A” may represent an enzyme, “B” a substrate, and “C” the product of the enzyme-catalyzed reaction. This reaction scheme may be generalized to involve more than two reactants.
Vesicles entrapping a single functionalized and encoded microparticle can also be prepared by methods known to the art. Using methods of this invention, microparticle encoded, gel-embedded vesicle arrays may be prepared to provide a synthetic assay format in which the function of multiple cell-surface receptors such as ion channels may be quantitatively characterized.
A variety of complex biochemical assays may be performed using such a composite structure. As illustrated in FIG. 17 , an array of vesicles displaying multiple types of receptors is immobilized in a thin gel film using methods disclosed herein. In this embodiment, each vesicle displays only one type of receptor and contains a corresponding fluorescently stained and functionalized microparticle. In the course of performing the assay, the fluorescent color of the particle is used to determine the identity of the receptor on the vesicle. In addition, the microparticle is also functionalized on its surface with a measuring element, such as an environmentally sensitive fluorescent dye, in order to indicate a change in the internal aqueous compartment of the vesicle following a binding event on its surface.
Patterned Materials
The ability to grow complex materials with small feature sizes is of much interest for the fabrication of structured and multifunctional films, biologically relevant heterostructures and photonic materials for optical and optoelectronic applications. Thus, processes to form patterns rapidly and directly to give geometrically as well as functionally organized structures without using complicated etching process or complicated chemical schemes can be extremely useful. In accordance with the present invention, the LEAPS-directed formation of patterned gel and gel-particle composites provides for the fabrication of a variety of inorganic-organic, organic-organic, or fully inorganic composite structures.
Organic-organic composite—After formation of the patterned gel film on the low impedance areas of the substrate, the high impedance regions of the substrate can be decorated with a second polymer preferably through a process other than bulk radical polymerization (employed to synthesize the gel). For example, if the substrate is silicon, regions of high and low impedance can be obtained by forming a patterned silicon oxide film on the surface of the silicon substrate. In this case, the regions where the oxide layer is relatively thicker correspond to regions of higher impedance. The high impedance silicon oxide-capped regions can be modified by covalently bonding siloxane polymers or oligomers, adsorbing polyelectrolytes, and/or adsorbing functional groups that are hydrophobic or capable of hydrogen bonding. Following such a process, the earlier gel layer can be lifted off, producing a complementary patterned polymer or gel film.
Organic-inorganic composite— FIG. 8 outlines the basic procedure for making metal (Au, Ag, Cu, etc.), metal oxide (Fe 2 O 3 , Co 3 O 4 , NiO) or semiconductor (CdS, PbS, ZnS) nanoparticles in the patterned gel matrix. The process involves exposing the patterned gel on a substrate to a solution of a metal salt, followed by DI water rinse and exposure to reducing agent (in case of the metal) or second salt solution in other cases. The nucleation and growth of the nanoparticles take place within the hydrophilic domains defined by the gel film.
Inorganic composite—Fully inorganic structures can be generated from the structures above by calcining at high temperatures so as to burn off the organic component.
Interconnections
The realization of interconnections in the form of electrical, optical, or chemical conduits in small devices represents a critical aspect of the realization of integrated electronic, optoelectronic, or biochemical processors and apparatus. The method of the present invention permits the assembly of linear microparticle assemblies in accordance with LEAPS, either under illumination or on patterned electrolyte-insulator-semiconductor (EIS) interfaces, and their subsequent immobilization, for example by embedding within a gel matrix as described herein.
Electrical Conduit—Following the assembly of metal core/polymer shell particles into linear configurations, rapid heating of the silicon substrate, for example by exposure to pulsed laser light, will melt away the polymer components and fuse adjacent metal cores. Of interest in this application will be particles containing solid metal (Cu, Ni) cores or particles containing metal nanoclusters dispersed into a polymer matrix which may be prepared by methods known to the art.
Optical Conduit—Within a linear assembly of glass particles, illuminated with focused light, particles will guide scattered or emitted light to their respective nearest neighbors. Thus, individual beads that are illuminated by focused laser light can serve as secondary sources to illuminate adjacent particles within the linear assembly.
Chemical Conduit—Following the assembly of polymer particles into linear, circular or other desired configurations, particles may be permanently immobilized on the substrate, for example by non-specific adsorption. The resulting structure may serve as a positive mold around which a gel matrix can be grown. When the gel matrix is then lifted, a complementary negative surface relief is revealed. Such structures can be closed by fusion with a substrate or another gel and can serve as linear conduits for the transport of biomolecules or other materials.
Self-Supporting Flipped and Cleaved Gels and Polymer-Microparticle Films
The present invention provides novel patterned films and/or polymer-microparticle composites, including a planar assembly or array of particles embedded in a gel (i.e., a single layer, or substantially single layer assembly). In preferred embodiment, these gels are prepared according to the methods described above.
As discussed previously, the patterned polymeric films and the polymer-microparticle composites of various types may be produced, for example, by varying the monomer concentration.
In one embodiment of the present invention, a self-supporting film (preferably a hydrogel) is prepared. In one example, the concentration of monomers in the polymerization is greater than about 10% by weight. Preferably, acrylamide monomers are used. Following the polymerization, the LEAPS microcell may be dismantled with the gel matrix attached to the first electrode. The hydrogel produced is self-supporting and a free-standing patterned gel film may be obtained simply by peeling off the film from the second electrode. The film is stable in aqueous solution and stays intact for months. An example of such a free standing gel is shown in FIG. 2 b . In addition to the substrate-supported and self-supporting gel films described above, a “Lift-Off” processes may be used to obtain polymeric films and/or composites that are detached from the light-sensitive (or patterned) bottom electrode. In one example, a vinyl siloxane coated second electrode is in the microcell. The vinyl siloxane coating allows covalent tethering of the gel film on the second electrode. Beads, suspended in a solution containing all ingredients required for subsequent in-situ gel formation, are assembled in designated regions of the light-sensitive (or patterned) electrode using an AC-electric field at a given voltage and frequency.
Keeping the field switched on, the microcell may, for instance, be irradiated with UV-light from a 150 W Hg source for about 3 minutes. Afterwards, the UV illumination and field are switched off and the microcell is opened by separating the first electrode from the second electrode: the covalent attachment of the gel to the second electrode ensures that the gel remains adhered to the second electrode and readily separates from the first electrode. By inverting the substrate-attached gel film, beads displaying receptors capable of binding the molecules of interest are located at the outer, exposed surface of this inverted or “flipped” gel (“FlipGel”). Thus, the diffusion length of the molecules to migrate from the solution above the gel to the bead surface is small compared to that in the case of non-inverted regular gels (see FIG. 4 a ). An assay then may be conducted on the gel-embedded bead array by exposing the gel to the solution containing analyte molecules of interest.
In certain other embodiments, the position of the bead array relative to the outer bounding surface of the embedding gel film may be controlled by assembling the microparticle array on a topographically patterned electrode surface. In these embodiments, designated recesses of defined depth containing a non-aqueous phase that is non-miscible with an overlaid aqueous phase containing the microparticles are exposed. The non-aqueous phase is also non-miscible with the chemical constituents required for gel film formation in accordance with the previous protocols (see FIG. 4 b ). Upon application of the requisite AC electric field, microparticles assemble within the designated recesses in such a way as to permit particles to remain partially submerged within the organic phase deposited into the recesses prior to assembly. Following assembly, gel formation is initiated in the manner described; however, the immiscibility of the two layered phases ensures that polymerization is confined to the aqueous phase, thereby leaving embedded microparticles partially exposed
In certain other embodiments, a cleaved gel is prepared, following the same principle as FlipGels. The basic differences are that (a) the monomer concentrations used in the polymerization reaction are smaller (for example, ≦5% by weight) and (b) the time of irradiation is shorter. Under these conditions, the degree of polymerization is not uniform throughout the thickness of the cell. Typically, the degree of polymerization and crosslinking is highest near the second electrode and progressively grows weaker as one approaches the first electrode. After gelling, disassembling the microcell, and pulling the two electrodes apart, the gel typically fractures at a plane very close to the substrate surface (see FIG. 5 ). Thus, a layer of gel remains attached to the second electrode while the first electrode retains the rest of the gel containing the assembled bead arrays. The first electrode, with the assembled bead array, can now be used for a variety of assays with the assay solution location directly on top of the bead-containing gel. In this application, the diffusion length of the molecules is reduced from that of a regular gel because the cleavage usually occurs just over the plane containing the bead array, leaving the beads more accessible to molecules present in the solution above the gel.
DNA Electrophoresis and Hybridization in Gel-Microparticle Hybrid Films
One method of performing rapid nucleic acid hybridization assays in gel-microparticle hybrid films involves the use of DC electric fields to induce electrophoresis of target nucleic acid strands. This method is especially suitable in applications where large target fragments are present for which diffusion inside the gels is expected to be slow. Typically the samples for analysis are denatured and electrophoresed through gel-microparticle hybrid films. As the complementary single-stranded nucleic acid targets contact the capture probe (oligo) functionalized beads, they hybridize and are quantitatively immobilized on the microparticle surface. The non-complementary strands do not hybridize with the capture probe and continue to migrate through the gel. The hybridization is detected using luminescent labels associated with the sample nucleic acid. FIG. 11 shows two different possible geometries for carrying out electrophoretically assisted hybridization in gel-microparticle hybrid films.
Reversible Immobilization of Microparticles within Gel Films
The process of forming polymeric films and polymer-composites involves synthesis of chemically crosslinked polymers. The process of forming composite gel-particle films according to this invention can, however, easily be extended to include physically gelling systems such as block copolymer gels, agarose gels, gelatin gels etc. Such gels consist of polymeric networks held together by physical rather than chemical crosslinking. The reversible gelation of such systems may, for example, be triggered thermally with the system existing as a sol at a high temperature and transforming into a gel on cooling and vice versa. The reversibility and the capability to form and to immobilize bead arrays at will allows one to carry out dynamic on-chip bioassays.
The flowchart in FIG. 7 summarizes one possible protocol for performing an assay using a reversible gel. The protocol begins with the formation of a bead array in the presence of a solution that contains a gel-forming agent. After the bead array is formed (for example using LEAPS as disclosed in U.S. Pat. No. 6,251,691), a gel is formed to immobilize the beads. Further processing steps, such as peeling to produce a Cleaved Gel or a FlipGel may be optionally performed prior to introducing the reaction mixture for the assay. After the assay, the gel is washed and the reaction products are detected, for example by monitoring a fluorescent signal that indicates the presence or absence of a particular reaction. A method of detection known as READ may be used, as described below. After detection, the gel is destroyed to liberate the beads in the gel. Following a subsequent washing step, the beads may be used again in other reversible gel assays. One method of performing the detection step in FIG. 7 is to use a protocol known as READ (Random Encoded Array Detection), as described in detail in PCT/US01/20179 hereby incorporated by reference). In this method, an image of the bead array is taken before the assay (i.e, a decoding image) and compared with an image of the bead array taken after the assay (i.e., an assay image). The decoding image is taken to determine the chemically and/or physically distinguishable characteristic that uniquely identifies the binding agent displayed on the bead surface, e.g., determining the identity of the binding agents on each particle in the array by the distinguishable characteristic. The assay image of the array is taken to detect the optical signature of the binding agent and the analyte complex. In certain embodiments, fluorescent tags (fluorophore dyes) may be attached to the analytes such that when the analytes are bound to the beads, the fluorescent intensities change, thus providing changes in the optical signatures of the beads. In certain embodiments, the decoding image is taken after the beads are assembled in an array and immobilized and before taking the assay image, preferably before contacting the binding agents on the beads with an analyte.
The identity of the binding agent of the binding agent-analyte complex is carried out by comparing the decoding image with the assay image.
In preferred embodiments, images analysis algorithms that are useful in analyzing the data obtained from the decoding and the assay images may be used to obtain quantitative data for each bead within an array. The analysis software automatically locates bead centers using a bright-field image of the array as a template, groups beads according to type, assigns quantitative intensities to individual beads, rejects “blemishes” such as those produced by “matrix” materials of irregular shape in serum samples, analyzes background intensity statistics and evaluates the background-corrected mean intensities for all bead types along with the corresponding variances.
EXAMPLES
The present invention will be better understood from the Experimental Details and Examples which follow. However, one skilled in the art will readily appreciate that the specific methods and results discussed are merely illustrative of the invention described in the claims which follow thereafter.
Example 1
AC Electric Field-Mediated Formation of Patterned Gel Films
LEAPS is carried out in a fluidic microcell formed by sandwiching a double-sided Kapton spacer of ˜100 μm thickness (between a 1 cm×1 cm silicon chip, n-type, capped either by a uniform or a lithographically patterned thin SiO 2 layer), also serving as the bottom electrode, and a glass cover slip coated with indium tin oxide (ITO) to a typical sheet resistance of 1400 Ohm Square serving as the top electrode. FIG. 1 illustrates the various components of a LEAPS microcell.
The mixture of monomers and the initiator is introduced within the LEAPS cell and the electric field is applied. The thermal free radical polymerization is then initiated by heating the cell ˜40–45° C. using an IR lamp (the polymerization can also be triggered by a step change in the bias voltage from a large positive value to a small positive value). Typical parameters of the AC electric field used for this particular example are Vp-p˜5–8V and ω˜1 kHz. This AC electric field-mediated protocol leads to the formation of a thin layer of hydrogel in predesignated areas (low impedance regions) on a Si/SiO 2 substrate.
Hydrogels are formed using azodiisobutyramidine dihydrochloride as a thermal initiator at a low concentration ensuring that the overall ionic strength of the polymerization mixture falls in the range of ˜0.01 mM to 0.1 mM. The hydrogels are composed of a mixture of acrylamide and bisacrylamide of varying monomer concentrations from 20% to 5% (acrylamide: bisacrylamide=37.5: 1, molar ratio).
FIG. 2 illustrates a hydrogel formed on an interfacially patterned silicon substrate under the influence of an AC electric field. The gel is formed exclusively in the low impedance regions (thin oxide) of the substrate. The wrinkled pattern seen on the hydrogel surface is caused by a mechanical instability set up in the gel during polymerization (Tanaka, T., 1987, Nature, 325:796; Warren, J. A., 1995, Spatio-Temporal Patterns, Ed. Cladis, P. E. and Palffy-Muhoroy, Addison-Wesley. 91–105).
Example 2
Preparation of Gel-Microparticle Hybrid Films
A two stage process is used to synthesize polymer-microparticle composites. First, ordered particle arrays are formed from a microparticle suspension that also contains all of the ingredients required for subsequent in-situ gel formation in accordance with Example 1. LEAPS (see Example 1) is used to form arrays from particles suspended in a low viscosity dispersion of monomer(s) mixed with an initiator in accordance with Example 1. Second, gels are formed, either via heat-initiated in-situ polymerization (Example 1) to form spatially patterned hybrid gels (see FIG. 3( a )) or via UV-initiated in-situ polymerization to form monolithic hybrid gels (see FIG. 3( b )), as described below.
To assemble particle arrays, an AC voltage chosen in the range of 1–20 V p-p , with a frequency in the range of 100 Hz to several kilohertz is applied between the electrodes across the fluid gap. Fluid and particle transport and assembly are then monitored by video microscopy, which permits frame capture and digitization of frames for further analysis.
Prior to assembly, particles stored in buffer are centrifuged and washed with deionized and ultrafiltered (conductivity<50 S cm −1 ) distilled water three times. At the last wash, the monomer/crosslinker and initiator solution is added in an amount so as to maintain the original concentration of particles. The initiator and/or the salt concentration is maintained at ≦1 mM. The resulting particle suspension is applied to the LEAPS cell so as to fill the gap between the two electrodes Anionic and cationic particles ranging from 0.5 μm to 15 μm in diameter, composed of silica, modified polystyrene or other polymers and functionalized with a variety of chemical surface groups, as well as functionalized core-shell particles obtained from a variety of manufacturers are used.
Following array assembly, polymerization of the fluid phase is triggered in the presence of the applied AC voltage, by for example, using a mercury lamp source to effectively entrap the particle array within the gel. A wide range of wavelengths, spanning from about 250 nm to about 340 nm, is suitable for the polymerization. FIG. 3 shows an example of a particle array immobilized in a polyacrylamide matrix. The concentration of the monomers was 10% and the initiator used was a UV initiator Irgacure 2959® (2-hydroxy-4′-hydroxyethoxy-2-methylpropiophenone, Ciba Geigy, Tarrytown, N.Y.). The initiator was added to the monomer to give a 1.5% by weight solution.
Example 3
Self-Supporting Magnetic Gel Films
In one embodiment, free standing gel microparticle hybrid films similar to those described in the detailed description section are prepared according to the invention using functionalized and superparamagnetic microparticles or a mixture of superparamagnetic particles with (non-magnetic) color-encoded and functionalized microparticles. Incorporation of magnetically responsive particles permits the separation of the gel film from a solution containing a biological sample or samples by application of a magnetic field.
This is of particular benefit in carrying out multi-step biological assay protocols.
In a protocol involving the self supporting magnetic gel films of this invention ( FIG. 9 a ), an in-tube binding assay that probes analyte molecules in solution through their capture by receptors on beads is performed under conditions permitting the magnetic gel-microparticle film to remain in suspension ( FIG. 9 b ). Following completion of the assay, magnetic separation ( FIG. 9 c ), achieved by application of a magnetic field, permits the temporary immobilization of the gel film on a transparent surface of the reaction chamber. Following fluid and/or buffer exchange, all excess fluid is removed in the last step, leaving the hydrated gel film exfoliated on the transparent surface even in the absence of the magnetic field ( FIG. 9 d ). Images recording the results of the binding assay may now be obtained using a microscope. In a preferred embodiment, a coverslip is positioned above the film to prevent evaporation, which may lead to buckling of the film.
Example 4
Hybridization Assay in Gel-Microparticle Hybrid Films
DNA hybridization assays were conducted using oligonucleotide-functionalized particles embedded in gels. The oligonucleotide probe-coated particles were made as follows. Neutravidin-coated beads were washed thoroughly in salinated PBS of pH 7.4. The biotinylated probes were then added to the bead suspension and the mixture was incubated at room temperature for 90 min. The probe-coated beads are then stored in PBS solution containing 0.01% Triton.
The targets for DNA hybridization reactions can be either single-stranded or double-stranded molecules. Single-stranded DNA of a given length and sequence were synthesized chemically (Integrated DNA Technologies, Coralville, Iowa). A double stranded DNA target was produced from PCR-amplified products directly obtained from genomic DNA of patient samples. The PCR product was produced using fluorescence-labeled primers. After preparation, the primers were removed by a PCR purification kit (Qiagen) and the resultant solution was used in an assay. Single stranded DNA was prepared from a double stranded sample by digesting the antisense strand. For this purpose the antisense primers used in PCR amplification had a phosphate group at the 5′ end. A strandase enzyme was then used to digest the antisense primer. In either case, the DNA at the end of the process was suspended in Tris-EDTA buffer and the concentration was determined using UV optical density measurements.
Before hybridization, the double stranded DNA was denatured to yield single strands. To achieve this, the DNA was diluted with Tris EDTA buffer and heated in a sand bath at 95° C. for 1 min. It was stored in ice before use. It was then mixed with an equal volume of tetramethylammonium chloride to yield the desired concentration of DNA for the reaction.
Two types of beads, internally stained with different fluorescent dyes and each bearing a different probe, were used for the reaction. One of the probes used was a prefect match with the target strand while the other sequence was mismatched.
The beads were washed three times with distilled water and suspended in 5% monomer solution and initiator concentration as described earlier. The beads were assembled into arrays in a LEAPS cell using 4 V peak-to-peak AC voltage and frequency 500 Hz. After assembly, the cell was irradiated with UV light for about 3 min. This yielded a Flip Gel which was then used in a hybridization assay. The Flip Gel was attached (gel-side up) to a polished silicon wafer using single-sided tape. One microliter of target containing 100 ng/μl DNA was diluted using 24 μl of TE and 25 μl of 2× TMAC. From the resultant solution 10 μl was added to the gel for reaction. The wafer was enclosed in an air-tight wafer holding container, sealed and set on a shaker at 50 rpm in an oven at 55° C. The reaction proceeded for 30 min. At the end of the procedure, the gel was washed twice in 1× TMAC equilibrated at 55° C.
The gels were prepared for imaging by applying a coverslip on them. Bright field and Cy5 filtered images were recorded. To distinguish the two different types of particles in the arrays, images were also taken at two other color channels appropriate for the internal encoding dyes. The set of four images were then analyzed to determine the results of the assay (see FIG. 10 ).
Example 5
Immunoassay in Gel-Microparticle Hybrid Films
Protein assays are readily performed on supported gels, self-supporting gels, FlipGels and Cleaved Gels. An example of an immunoassay is the binding reaction between Mouse IgG and Goat Anti-Mouse IgG. For this reaction, the beads were surface-coated with the Mouse IgG. For this purpose, tosylated particles with a diameter of 3.2 μm were incubated overnight with the Mouse antibody (SigmaChem) in a phosphate buffer solution of pH 7.2. After the coating process, the particles are washed thoroughly with PBS containing bovine serum albumin.
The target molecules of goat anti-mouse IgG were labeled with a monofunctional fluorescent dye Cy5.5 (Amersham). The NHS-ester-containing dye was attached to the amine groups of the IgG according to a protocol supplied by the manufacturer. The dye and the IgG molecules were incubated for 1 hr at pH 9.3. The free dye was then separated from the labeled molecules using a gel filtration column and phosphate-buffered saline as the separation buffer. The concentration of IgG in the sample and the number of dye molecules per molecule of IgG was calculated.
Two types of particles are used for the reaction, one for the assay and the other as a negative control. They are distinguished by the use of internal encoding dyes which have excitation and emission wavelengths that are different from those of Cy5.5. One of the types of particles was coated with Mouse IgG as described above and the other only had a coating of neutravidin. A mixture of these two types of particles was collected by centrifugation and washed three times with de-ionized water containing 0.01% Triton. After the last centrifugation, the particles were suspended in a monomer mixture containing 10% monomer solution and UV-initiator in amounts described earlier. The particles were assembled in a LEAPS cell and irradiated to form a monolithic gel. Depending of the concentration and the time of irradiation, a regular gel, FlipGel or Cleaved Gel is formed.
The gel is placed with the support (coverslide in case of FlipGel, silicon chip in case of regular and Cleaved Gels) gel side up. A given volume (10 μl) of a known concentration of the Goat anti-Mouse IgG placed on the gel. The gel with the solution is then enclosed in an airtight container and put on a shaker operating at 50 rpm in an oven at 37° C. for one hour. After binding has occurred, the gel was loaded with 20 μl of alkaline SDS (Tris base containing 10% SDS) for 30 min to reduce nonspecific binding. The gel was then washed with alkaline SDS twice and prepared for imaging. A coverslip was placed on the wet gel and images were taken in the bright field and in the Cy5.5 channel. To distinguish the two different types of particles in the arrays, images were also taken at two other color channels appropriate for the internal encoding dyes. The images were then analyzed to establish the mean binding intensity and the light intensity distribution of each type of bead in the mixture (see FIG. 12 ).
Example 6
Bioanalytical Assay with Integrated Filtering and Specific Capture
The gel-microparticle hybrid film is useful for selectively capturing specific nucleic acids or proteins from a crude mixture like whole blood or cell lysate. Typically, a crude sample containing whole blood is placed in contact with the gel containing microparticles that are functionalized with capture probe molecules of interest. The red and white cells are automatically screened by the gel on the basis of their size. The complementary components from plasma bind to the capture probe coated beads. Non-complementary components can then be easily washed off.
Example 7
Recording of Assay Images from Hybrid Films
In this invention, a Nikon Eclipse E-600FN epifluorescence microscope equipped with 150 W xenon-arc lamp was used for measurements. A Nikon 20×0.75 NA air objective, fitted with an optimized set of filter cubes for the selection of fluorophores also was used for all measurements. Images were recorded with a cooled 16 bit CCD camera (Apogee Instruments Inc.). The exposure/integration times for the various preparations varied between 25 to 500 ms. User interfaced programs for collection and analysis of images and assay results were developed using MATLAB™ which was run on a PC.
Example 8
Multiple Samples Per Chip
FIG. 13 illustrates a method of carrying out multiplexed assays for multiple samples using the same monolithic gel film containing multiple bead arrays. A gel film containing bead arrays is synthesized (as described in Example 3) on an interfacially patterned silicon chip into which through holes have been made at four corners (choice of this geometry is arbitrary and is chosen here for illustrative purposes only. In principle, a wide variety of designs and number of holes can be chosen. The samples are added by pipette to the holes in the back of the chip. The sample is allowed to spread diffusively and to react with the surrounding particles as shown in FIG. 13 . Depending on the length of the incubation time the area of the reacted patch will vary (Area˜tD, where t is the reaction time and D is the diffusion coefficient of the target in gel).
Example 9
Cell-Based Heteroreactor
A cell-based heteroreactor of this invention is constructed on a silicon substrate containing etched through-holes serving as fluidic interconnects. First, a gel-microparticle composite is formed in accordance with Example 3 in the fluidic compartment defined by the front side of the silicon electrode and the ITO-coated glass electrode. Next, suspensions of cells are introduced into the tapered etched through-holes on the backside of the silicon electrode. Molecules secreted from cells within these microwell structures are allowed to diffuse into the gel, as shown schematically in FIG. 14 , where they are detected after being captured by functionalized beads within the previously assembled array. Alternatively, cells within the microwells may be lysed, and released genomic DNA may be enzymatically fragmented to allow sufficiently small fragments to diffuse into the gel where they are captured by hybridization to functionalized beads within the previously formed array. In this embodiment, constituents of the lysate that are larger than the pore openings of the gel are kept out. This second structure can remain open, and may be fashioned to exhibit the dimensions and form factors of various useful structures, such as a 1536-well microplate, for example. In other embodiments, a third delimiting planar substrate may be placed in contact with the back side of the silicon electrode, in order to form a second fluidic compartment that permits microfluidic transport of cell suspensions.
Example 10
Fabrication of an Enzyme Sensor by Directed Self-Assembly
In accordance with the methods of the present invention, the combination of LEAPS-mediated active assembly of an array of functionalized microparticles and the chemical synthesis of a polymeric gel film permits the in-situ synthesis of a variety of sensors.
Starting with a fluidic microreactor composed of a patterned silicon/silicon oxide chip and an ITO-coated glass electrode arranged in a sandwich geometry ( FIG. 1 ), a glucose sensor based on a gel-microparticle composite is constructed by the following sequence of steps.
1—inject solution containing
functionalized particles displaying pH-sensitive or oxygen-sensitive dyes known to the art reaction mixture containing precursors and ingredients for gel formation functionalized glucose oxidase
2—apply AC electric field according to LEAPS to produce microparticle arrays) 3—form gel by UV-initiated polymerization to form patterned or monolithic gel film incorporating functionalized glucose oxidase 4—remove electric field and UV illumination 5—inject glucose-containing sample into space below patterned silicon chip to initiate diffusion of sample into gel matrix; in the presence of glucose, the following reaction occurs
6—monitor reaction shown above by recording fluorescence intensity from microparticle array; reduced oxygen levels or the reduced pH in the local gel environment, as indicated by the bead-anchored dyes, serve as an indirect indication of glucose concentration.
In a preferred embodiment, the silicon electrode contains a set of access ports as illustrated in FIG. 13 . In the resulting sensor ( FIG. 16 ) the enzyme glucose-oxidase is immobilized covalently in the gel film, with microparticles functionalized or loaded with pH-sensitive or oxygen-sensitive fluorescent dyes.
Example 11
Gel-Embedded Cellular Arrays and Their Use in Cell-Based Functional Assays
The entrapment and immobilization of viable cells in various polymeric matrices, natural or synthetic, including polyacrylamide (Vorlop, K. et al. Biotechnol. Tech. 6:483 (1992)) have been reported, primarily in connection with biocatalysis (Willaert, P. G. et al. (Eds.), “Immobilized living cell systems: Modeling and experimental methods.” Wiley, New York, 1996). Polymeric matrices can provide a hydrated environment containing nutrients and cofactors needed for cellular activity and growth. To minimize mass transfer limitations, methods of the present invention may be used to immobilize arrays of cells in a thin and porous gel film.
In accordance with the methods of the present invention, the process of forming a composite structure containing cell arrays entrapped in a patterned or monolithic gel film consists of two stages. First, ordered cell arrays are formed from a cell suspension also containing all ingredients required for subsequent in-situ gel formation in accordance with Example 1. In a preferred embodiment of the array assembly process, LEAPS (Example 1) is invoked to form arrays from cells suspended in a low viscosity dispersion of monomer(s) mixed with an initiator in accordance with Example 1. Second, gels films are formed, either via heat-initiated in-situ polymerization to form a spatially patterned composite or via UV-initiated in-situ polymerization to form a monolithic composite, as described in Example 2.
The immobilized cell array system of this invention is useful for a variety of assay formats. For example, to analyze and quantify several molecular targets within a sample substance, the methods of this invention provide means to form a gel-embedded cell array displaying a plurality of receptors (to one or more of the targets) which may be exposed to the sample substance.
An alternative format of a functional assay, shown in FIG. 18 , involves the combination of a gel-microparticle heterostructure with a gel-embedded cellular array prepared by the methods of this invention. Embedding cells within a thin gel film facilitates the engineering of small, functionally organized heterostructures by avoiding the manipulation of individual cells while providing local chemistries capable of maintaining cells in their requisite environment. The lateral spacing of cells as well as microparticles within their respective arrays is readily tuned in such a structure using LEAPS as disclosed herein.
In an embodiment of this invention, two separate gel films, one containing a functionalized microparticle array and the other a cellular array, are placed in direct contact in a sandwich geometry. In this configuration, particles and cells form pairs of sources and detectors of molecules to be analyzed. For example, cells can secrete molecules such as cytokines, and proximal beads within the bead array can be designed to monitor the profile, for example in a displacement assay. Alternatively, small molecules can be photochemically cleaved from an array of color-encoded beads and can be detected by monitoring the functional response of cells within the apposed gel-embedded array. The lateral patterning of the arrays as well as the short diffusion length in the vertical direction helps to prevent lateral mixing of the ligand molecules and hence enables execution and monitoring of complex local binding chemistries.
Example 12
Characterization and Control of Diffusive Transport in Gels
The diffusion of fluorescently tagged molecules into the gels of the present invention were studied using a sandwich cell device as illustrated in FIG. 19 a. To provide actual chemical anchoring of the gel to both the Si-chip surface and the glass coverslip both of them were pretreated using vinylmethoxysiloxane oligomer for polyacrylamide gels, and 3-(glycidoxypropyl)-trimethoxysilane for agarose gel, respectively.
For the coating reaction a 95% ethanol and 5% water solution was adjusted to pH 5 with acetic acid. The silane coupling agent was then added to yield a 2 wt % solution. Substrates (chips and cover glasses) were dipped into the solution with gentle agitation for 5 minutes. Following, the substrates were removed from the solution and rinsed briefly in ethanol. The treated substrates were cured at room temperature for 24 hours.
For the formation of the acrylamide gels the monomer mixture of 10% (w/v) acrylamide, 3% (w/v) NN′-methylene-bis-arylamide (Polysciences, Ltd, USA), 0.1% photo initiator 1-[4-2-Hydroxyethoxy)-phenyl]2-hydroxy-2-methyl-1-propane-1-one (IRGACURE® 2959, Ciba Specialty Chemicals (USA)) as well as H 2 O was injected into the sandwich cell. The masked cell was then exposed to a UV light source (150 W Hg lamp) through a photo-mask for durations ranging from 45 s to 180 s. Following the exposure, the unpolymerized solution was removed from the cell.
For agarose gel formation, one microliter of an agarose solution (0.5% w/v) (heated to ˜90° C.) was carefully added to the surface of a pretreated Si chip by pipette, and gently covered with a pretreated cover glass slide. Under these conditions the drop of the agarose sol deformed into an approximately cylindrical plug sandwiched between the two surfaces, and turned into a gel under room temperature condition within 1–2 minutes. Once formed, the gel was left undisturbed at room temperature for additional 2–3 hours to promote covalent crosslinking between the hydroxyl groups in the agarose chains and the epoxy group present on the pretreated surfaces.
Example 13
Polymer-Microparticle Composites Using a Thermally Reversible Gel
The microparticles were assembled in a 0.5% to 0.15% Ultrapure Agarose solution (Melting temperature˜65° C., Sigma-Aldrich, St. Louis, Mo.), using a temperature-controlled sandwich cell maintained at ˜55° C. The method of assembly was as described in the earlier examples. After the array assembly was complete (1–3 minutes), the heater was switched off and the whole assembly was cooled down rapidly to about 5° C. using a cold air gun. This cooling induced the formation of an agarose gel. The microparticle arrays that were embedded in the agarose gel ( FIG. 20 a ) were further used in hybridization-based assays as described below.
Oligo(dT) 25 -coupled magnetic particles (2.8 μm, Dynal, Norway) were used to create agarose gel embedded microparticle arrays in a sandwich cell as described above. The sample (20 μl of hybridization mixture containing Cy5-labeled 100 bp-long complementary target, 50 μM) was applied to the film and incubated at 55° C. for 30 minutes. Following the reaction, the film was washed once with TMAC and the light intensity distribution of the microparticles in the gel was analyzed (see Example 7). The resulting histogram and data are shown in FIG. 20 b.
Two different types of Oligo probe-coupled particles (3.2 μm, Bangs Labs, Ind.), (one complementary to a PCR fragment and the other noncomplementary to the target) were used in an extension-based hybridization assay using a FlipGel format. An aliquot of 10 μl of a 100 nM solution of the target (280 bp PCR fragment) in annealing buffer of 0.2 M NaCl, 0.1% Triton X-100, 10 mM Tris/pH 8.0, 0.1 mM EDTA was applied to the gel and allowed to react for 15 min at 30° C. The gel was then washed once with the same buffer and was then covered with an extension reaction mixture that comprised the following: 100 nM of TAMRA-ddCTP (absorption/emission: 550/580 nm) (PerkinElmer Bioscience, Boston, Mass.), and 10 μM dATP-dGTP-dTTP, ThermoSequenase (Amersham, Piscataway, N.J.) in the associated buffer supplied by the manufacturer. The reaction was allowed to proceed for 5 min at 60° C., and the chip was then washed in H 2 O. Decoding and assay images of the chip were acquired as described before (Example 7). The results are shown in FIG. 20 c.
Although a few exemplary embodiments of this invention have been described in detail above, those skilled in the art will appreciate that many modifications of the preferred embodiments are possible using the novel teachings and advantages of this invention. Accordingly all such modifications are intended to be included within the scope of this invention, as defined in the following claims. | The present invention relates to a systematic process for the creation of functionally organized, spatially patterned assemblies of polymer-microparticle composites including the AC electric field-mediated assembly of patterned, self-supporting organic (polymeric) films and organic-polymer-microparticle composites of tailored composition and morphology. The present invention further relates to the incorporation of said assemblies into other structures. The present invention also relates to the application of such functional assemblies in materials science and biology. Additional areas of application include sensors, catalysts, membranes, and micro-reactors, and miniaturized format for generation of multifunctional thin films. This invention also provides simple methods and apparatus for synthesizing thin films of tailored composition and morphology. | 2 |
TECHNICAL FIELD
[0001] The present disclosure relates in general to information handling systems, and more particularly to power control of information handling system devices.
BACKGROUND
[0002] As the value and use of information continues to increase, individuals and businesses seek additional ways to process and store information. One option available to users is information handling systems. An information handling system generally processes, compiles, stores, and/or communicates information or data for business, personal, or other purposes thereby allowing users to take advantage of the value of the information. Because technology and information handling needs and requirements vary between different users or applications, information handling systems may also vary regarding what information is handled, how the information is handled, how much information is processed, stored, or communicated, and how quickly and efficiently the information may be processed, stored, or communicated. The variations in information handling systems allow for information handling systems to be general or configured for a specific user or specific use such as financial transaction processing, airline reservations, enterprise data storage, or global communications. In addition, information handling systems may include a variety of hardware and software components that may be configured to process, store, and communicate information and may include one or more computer systems, data storage systems, and networking systems.
[0003] During operation of an information handling system, numerous events may occur in which the available power from power supplies delivering electrical current to the information handling system and its components may decrease. To ensure effective operation of an information handling system after such a decrease in available power, it may be desired to reduce the power requirements (“throttle”) of one or more components of the information handling system, particularly such components that require higher levels of power during normal operation. When throttled, a component may enter a lower-power state in which it decreases functionality (e.g., processing and transfer of data at slower rates) but consumes less power.
[0004] Traditionally, throttling of information handling system components has been performed by software. However, software-based throttling often requires significant time between the time a throttling stimulus is received and a throttling occur due to processing overhead associated with software.
SUMMARY
[0005] In accordance with the teachings of the present disclosure, the disadvantages and problems associated with controlling power usage of devices in information handling systems, and in particular throttling of devices in information handling systems, have been reduced or eliminated.
[0006] In accordance with teachings of the present disclosure, a device for use in an information handling system may include a connector and an auxiliary power connector. The connector may be configured to electrically couple to a device connector such that the device transmits and receives data via the device connector and receives electrical current from a power supply via the device connector. The auxiliary power connector may be configured to electrically couple the device to the power supply such that the device receives electrical current from the power supply via the device connector, the auxiliary power connector including at least one sense line, the at least one sense line configured to receive at least one power control signal. The device may be configured to establish its power usage in response to receiving the at least one power control signal.
[0007] In accordance with additional teachings of the present disclosure, an information handling system may include a processor, a power supply, power control logic, and a device. The power control logic may be configured to determine whether a stimulus has been received indicative of a power availability of the power supply and transmit at least one power control signal in response to receiving the stimulus. The device may be electrically coupled to the power supply via a device connector such that the device transmits data to and receives data from the processor via the device connector and receives electrical current from a power supply via the device connector, the device comprising an auxiliary power connector configured to electrically couple the device to the power supply such that the device receives electrical current from the power supply via the device connector. The auxiliary power connector may include at least one sense line, the at least one sense line configured to receive the at least one power control signal. The device may be configured to establish its power usage in response to receiving the at least one power control signal.
[0008] In accordance with further teachings of the present disclosure, a method may include transmitting and receiving data at a device via a device connector. The method may also include receiving electrical current at the device from a power supply via the device connector. The method may additionally include receiving electrical current at the device from a power supply via the auxiliary power connector. The method may further include receiving at least one power control signal at the device via at least one sense line of the auxiliary power connector. Moreover, the method may include establishing power usage for the device in response to receiving the at least one power signal.
[0009] Other technical advantages will be apparent to those of ordinary skill in the art in view of the following specification, claims, and drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] A more complete understanding of the present embodiments and advantages thereof may be acquired by referring to the following description taken in conjunction with the accompanying drawings, in which like reference numbers indicate like features, and wherein:
[0011] FIG. 1 illustrates a block diagram of an example information handling system, in accordance with certain embodiments of the present disclosure; and
[0012] FIG. 2 illustrates a flow chart of an example method for controlling power usage of device of an information handling system, in accordance with certain embodiments of the present disclosure.
DETAILED DESCRIPTION
[0013] Preferred embodiments and their advantages are best understood by reference to FIGS. 1 and 2 , wherein like numbers are used to indicate like and corresponding parts.
[0014] For the purposes of this disclosure, an information handling system may include any instrumentality or aggregate of instrumentalities operable to compute, classify, process, transmit, receive, retrieve, originate, switch, store, display, manifest, detect, record, reproduce, handle, or utilize any form of information, intelligence, or data for business, scientific, control, entertainment, or other purposes. For example, an information handling system may be a personal computer, a PDA, a consumer electronic device, a network storage device, or any other suitable device and may vary in size, shape, performance, functionality, and price. The information handling system may include memory, one or more processing resources such as a central processing unit (CPU) or hardware or software control logic. Additional components or the information handling system may include one or more storage devices, one or more communications ports for communicating with external devices as well as various input and output (I/O) devices, such as a keyboard, a mouse, and a video display. The information handling system may also include one or more buses operable to transmit communication between the various hardware components.
[0015] For the purposes of this disclosure, information handling resources may broadly refer to any component system, device or apparatus of an information handling system, including without limitation processors, busses, memories, input-output devices and/or interfaces, storage resources, network interfaces, motherboards, electro-mechanical devices (e.g., fans), displays, and power supplies.
[0016] For the purposes of this disclosure, computer-readable media may include any instrumentality or aggregation of instrumentalities that may retain data and/or instructions for a period of time. Computer-readable media may include, without limitation, storage media such as a direct access storage device (e.g., a hard disk drive or floppy disk), a sequential access storage device (e.g., a tape disk drive), compact disk, CD-ROM, DVD, random access memory (RAM), read-only memory (ROM), electrically erasable programmable read-only memory (EEPROM), and/or flash memory; as well as communications media such wires, optical fibers, microwaves, radio waves, and other electromagnetic and/or optical carriers; and/or any combination of the foregoing.
[0017] FIG. 1 illustrates a block diagram of an example information handling system 100 , in accordance with certain embodiments of the present disclosure. In certain embodiments, information handling system 100 may comprise a computer chassis or enclosure (e.g., a server chassis holding one or more server blades). In other embodiments, information handling system 100 may comprise a storage enclosure. In yet other embodiments, information handling system 100 may be a personal computer (e.g., a desktop computer or a portable computer). As depicted in FIG. 1 , information handling system 100 may include a processor 103 , a memory 104 , a power supply 106 , a device connector 108 , a device 110 , information handling resources 116 , and power control logic 118 .
[0018] Processor 103 may include any system, device, or apparatus configured to interpret and/or execute program instructions and/or process data, and may include, without limitation a microprocessor, microcontroller, digital signal processor (DSP), application specific integrated circuit (ASIC), or any other digital or analog circuitry configured to interpret and/or execute program instructions and/or process data. In some embodiments, processor 103 may interpret and/or execute program instructions and/or process data stored in memory 104 and/or another component of information handling system 100 . Although FIG. 1 depicts information handling system 100 as including one processor 103 , information handling system 100 may include any suitable number of processors 103 .
[0019] Memory 104 may be communicatively coupled to processor 103 and may include any system, device, or apparatus configured to retain program instructions and/or data for a period of time (e.g., computer-readable media). Memory 104 may include random access memory (RAM), electrically erasable programmable read-only memory (EEPROM), a PCMCIA card, flash memory, magnetic storage, opto-magnetic storage, or any suitable selection and/or array of volatile or non-volatile memory that retains data after power to information handling system 100 is turned off. Although FIG. 1 depicts information handling system 100 as including one memory 104 , information handling system 100 may include any suitable number of memories 104 .
[0020] Power supply 106 may be electrically coupled to various components of information handling system 100 and may include any device, system, or apparatus operable to supply electrical energy to one or more components of information handling system 100 . Although FIG. 1 depicts information handling system 100 as including one power supply 106 , information handling system 100 may include any suitable number of power supplies 106 .
[0021] Device connector 108 may be communicatively coupled to processor 103 and electrically coupled to power supply 106 , and may be configured to receive a device 110 . In some embodiments, device connector 108 may be an integral portion of a motherboard upon which other components of information handling system (e.g., processor 103 , connectors for memory 104 , etc.) are mounted. In these and other embodiments, device connector 108 may comprise a Peripheral Component Interconnect (PCI) expansion slot.
[0022] Device 110 may be a printed circuit board or other device that may be inserted or otherwise mechanically and electrically coupled to device connector 108 in order to add functionality to information handling system 100 . Device connector 108 may establish electrical contact between device 110 and other components of information handling system 100 (e.g., processor 103 and power supply 106 ) such that device 110 may receive electrical current from power supply 106 via device connector 108 and/or may transmit and/or receive data from processor 103 via device connector 108 . For example, in embodiments in which device 110 comprises a printed circuit board, one edge of the printed circuit board may include an edge connector having electrically conductive contacts that fit into device connector 108 which establish electrical contact between electronics (e.g., integrated circuits) on device 110 and electronics on a motherboard. In some embodiments, device 110 may comprise a Peripheral Component Interconnect (PCI) expansion card. In the same or alternative embodiments, device 110 may include a general purpose graphics processing unit (GPGPU).
[0023] As shown in FIG. 1 , device 110 may include one or more auxiliary power connectors 112 . An auxiliary power connector 112 may be configured to receive corresponding connectors via which electrical current may be supplied from power supply 106 , thus allowing device 110 to draw current from power supply 106 via device connector 108 and auxiliary power connectors 112 . A power connector 112 may also be associated with a sense line 114 , as shown in FIG. 1 . In some embodiments, power drawn via device connector 108 may remain available regardless of the available power of power supply 106 , while the maximum power drawn via auxiliary power connectors 112 may be variable and/or may be adjusted based on the available power of power supply 106 , as described in greater detail below.
[0024] Sense lines 114 may be communicatively coupled to power control logic 118 , thus permitting device 108 to receive control signals from power control logic 118 , as described in greater detail below.
[0025] Information handling resources 116 may be communicatively coupled to processor 103 and may include any component system, device or apparatus of an information handling system, including without limitation processors, busses, memories, input-output devices and/or interfaces, storage resources, network interfaces, motherboards, electro-mechanical devices (e.g., fans), displays, and power supplies.
[0026] Power control logic 118 may be communicatively coupled to various components of information handling system 100 and may comprise any system, device, or apparatus configured to receive one or more stimuli indicative of a power availability for power supply 106 and adjust the power usage of device 110 in response to such stimuli. Examples of stimuli are described below in connection with the discussion of method 200 . In some embodiments, power control logic 118 may include a complex programmable logic device (CPLD).
[0027] The operation of components of information handling system 200 may be illustrated by FIG. 2 . FIG. 2 illustrates a flow chart of an example method 200 for controlling power usage of device (e.g., device 110 ), in accordance with certain embodiments of the present disclosure. According to one embodiment, method 200 may begin at step 202 . As noted above, teachings of the present disclosure may be implemented in a variety of configurations of system 100 . As such, the preferred initialization point for method 200 and the order of the steps 202 - 212 comprising method 200 may depend on the implementation chosen.
[0028] At step 202 , power control logic 118 may receive stimulus indicative of a power availability for power supply 106 and/or power usage of components of information handling system 100 . In some embodiments, such stimulus may be received at startup or power on of information handling system 100 or as part of an initialization of power control logic 118 and/or another component of information handling system 100 . Among the stimuli that may be received by power control logic 118 include, without limitation:
temperature conditions of power supply 106 or its components (e.g., voltage regulators); events associated with memory (e.g., temperature conditions associated with memory); commands from node manager management engine or a datacenter manager; alerts associated with power supply 106 (e.g., output overcurrent warning, overtemperature warning, undervoltage warning); parameters from current monitors and/or power monitors for components of information handling system 100 indicative of power draw/power requirements of such components; commands received from an access controller (e.g., Integrated Dell Remote Access Controller); and commands received from a chassis management controller).
[0036] At step 204 , power control logic 118 may communicate one or more control signals to device 110 via sense lines 114 in response to receipt of the stimulus. In some embodiments, such control signals may be indicative of the amount of power (e.g., a maximum power availability) to be used by device 110 . In these embodiments, such amount may be determined based on the power availability of power supply 106 , the power usage and/or power requirements of other components of information handling system 100 , and/or any other parameters.
[0037] At step 206 , device 110 may set its power usage in response to receipt of the one or more control signals. For example, based on the received control signal(s), device 110 may set a maximum amount of power to be drawn by the device 110 via auxiliary power connectors 112 .
[0038] At step 208 , power control logic 118 may determine whether a stimulus has been received indicative of a change in power availability for power supply 106 and/or power usage of components of information handling system 100 . In some embodiments, such change may be a reduction in the power availability of power supply 106 . If a stimulus indicative change has been received, method 200 may proceed to step 210 . Otherwise, if such a stimulus has not been received, step 208 may repeat until such stimulus is received. The stimuli indicative of a change in power availability or power usage may be the same or similar to those described above in reference to step 202 .
[0039] At step 210 , power control logic may communicate one or more control signals to device 110 via sense lines 114 in response to stimulus indicating a change in power availability. As in step 204 , such control signals may be indicative of the amount of power (e.g., a maximum power availability) to be used by device 110 and such amount may be determined based on the power availability of power supply 106 , the power usage and/or power requirements of other components of information handling system 100 , and/or any other parameters.
[0040] At step 212 , device 110 may adjust its power usage in response to receipt of the one or more control signals. In instances in which the control signals arise as a result of a reduction in available power of power supply 106 , device 110 may reduce its power usage. For example, based on the received control signal(s), device 110 may adjust a maximum amount of power to be drawn by the device 110 via auxiliary power connectors 112 . In some embodiments, such reduction in power usage and/or reduction in maximum power to be drawn via auxiliary power connectors 112 may be substantially instantaneous. After completion of step 212 , method 200 may proceed again to step 208 .
[0041] Although FIG. 2 discloses a particular number of steps to be taken with respect to method 200 , method 200 may be executed with greater or lesser steps than those depicted in FIG. 2 . In addition, although FIG. 2 discloses a certain order of steps to be taken with respect to method 200 , the steps comprising method 200 may be completed in any suitable order. In addition, the steps comprising method 200 may be repeated, independently and/or collectively, as often as desired or required by a chosen implementation.
[0042] Method 200 may be implemented using information handling system 100 or any other system operable to implement method 200 . In certain embodiments, method 200 may be implemented partially or fully in software and/or firmware embodied in computer-readable media.
[0043] Although the present disclosure has been described in detail, it should be understood that various changes, substitutions, and alterations can be made hereto without departing from the spirit and the scope of the disclosure as defined by the appended claims. | Systems and methods for controlling power usage of devices in information handling systems are provided. A device for use in an information handling system may include a connector and an auxiliary power connector. The connector may be configured to electrically couple to a device connector such that the device transmits and receives data via the device connector and receives electrical current from a power supply via the device connector. The auxiliary power connector may be configured to electrically couple the device to the power supply such that the device receives electrical current from the power supply via the device connector, the auxiliary power connector including at least one sense line, the at least one sense line configured to receive at least one power control signal. The device may be configured to establish its power usage in response to receiving the at least one power control signal. | 8 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to providing a business information service, and more particularly, to cleansing data associated with customer lists.
2. Description of the Related Art
Some potential business information service users have customer data that is not functioning at the maximum possible efficiency. This is because some critical data is missing, some addresses are wrong, and some of the customers have moved. These problems can affect internal databases preventing accurate identification of a customer coming in from a telecenter, mailroom, or website, leading to a creation of duplicates and possible mishandling the customer relationship. Response rates to mailed promotions may weaken as fewer customers actually receive them. There is a need for a business information service that cleanses data to provide accurate customer addresses.
Some services provide a mish-mash of many, often conflicting suggested changes for each address element. This makes leveraging corrections very difficult. There is a need for an output of a single best correction for each address element.
BRIEF SUMMARY OF THE INVENTION
The present invention is directed to a system and method for data cleansing that meets these and other needs.
There is provided a method that includes (a) receiving an input postal address, (b) comparing the input postal address to a standard, (c) providing a single best postal address corresponding to the input postal address based on the comparing, (d) matching the single best postal address to a business in a business information database, (e) obtaining a business address for the business from the business information database, and (f) correcting the single best postal address, based on the business address, to yield a corrected postal address.
In another method, at least one input address is received. The input address is compared to at least one standard and a single best address corresponding to the input address is provided based on the comparison. In some embodiments, the single best address is matched to a database having unique business identifiers associated with addresses to find a matching address, which is provided. In some embodiments, the database is an advanced office system (AOS). In some embodiments, a match project analysis report is provided. In some embodiments, the input address is converted to a predetermined record layout, before comparing it to the standard. In some embodiments, the input address is associated with at least one code that is used to determine the single best address. In some embodiments, the input address is associated with at least one score that is used to determine the single best address. In some embodiments, the standard is at least one of the following: ZIP+4 coding, coding accuracy support system (CASS), Locatable Address Conversion System (LACS), delivery sequence file (DSF), and National Change of Address (NCOA). In some embodiments, a report is provided. In some embodiments, the report is a postal summary report or a pre-audit report. In some embodiments, at least one status notification is sent to the user, who supplied the input address.
There is also provided a system that includes (a) a pre-auditor that generates a report having a plurality of views of an input address file, the input address file including a record having an input postal address, (b) a component that compares the input postal address to a file of standardized postal addresses, and provides a single best postal address derived from the input postal address, based on the comparison, (c) a matcher that matches the single best postal address to a business in a business information database, and obtains a business address for the business from the business information database, and (d) a component that corrects the single best postal address based on the business address, to yield a corrected postal address.
Another system includes a pre-auditor, a verifier, a vendor interface, and a user interface. The pre-auditor is for generating a report having a number of views of an input address file, which contains a plurality of addresses. The verifier is for finding and removing any invalid records from the input address file. The vendor interface is for sending the input address file and an order to at least one vendor and for receiving an output file from the vendor(s). The user interface is for providing a single best address for each address in the input address file. In some embodiments, the system includes a matcher for attempting to match any address in the output file or the invalid records to a matching address in a database that contains unique business identifiers associated with addresses. In some embodiments, the system includes an investigator for investigating any address not matched, upon request. In some embodiments, the pre-auditor calculates a plurality of counts associated with the input address file. In some embodiments, the input address file includes a plurality of records and each record includes a plurality of fields. In some embodiments, the counts are at least one of the following: a number of distinct values by field, a missing field count, a total number of records, or a percent of distinct values. In some embodiments, the views are one of the following: alphabetical, most frequent content, and alpha characters only. In some embodiments, the vendor standardizes addresses using one of the following: Locatable Address Conversion System (LACS), delivery sequence file (DSF), and National Change of Address (NCOA).
There is also provided machine-readable medium having instructions stored thereon that cause the machine to perform actions of (a) receiving an input postal address, (b) comparing the input postal address to a standard, (c) providing a single best postal address corresponding to the input postal address based on the comparing, (d) matching the single best postal address to a business in a business information database, (e) obtaining a business address for the business from the business information database, and (f) correcting the single best postal address, based on the business address, to yield a corrected postal address. A machine-readable medium is any storage medium, such as a compact disk (CD).
Another machine-readable medium having instructions stored thereon causes the machine to perform another method. At least one input address is received. The input address is compared to at least one standard and a single best address corresponding to the input address is provided based on that comparison. In some embodiments, the single best address is matched to a database having unique business identifiers associated with addresses to find a matching address and a matching address is provided.
These and other features, aspects, and advantages of the present invention will become better understood with reference to the drawings, description, and claims.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A and 1B are logic flow diagrams of an example method of data cleansing;
FIG. 2 is a logic flow diagram of another example method for data cleansing;
FIG. 3 is a logic flow diagram of the operation of an example system for data cleansing;
FIG. 4 is a logic flow diagram of an example vendor domestic address cleansing system; and
FIG. 5 is a logic flow diagram of an example vendor international hygiene system.
DETAILED DESCRIPTION OF THE INVENTION
FIGS. 1A and 1B show an example method of data cleansing. In step 100 , a project manager receives a user input file and file layout and uploads the file to a processor, such as a mainframe. In step 102 , the project manager sends an order with a product code to a vendor. In step 104 , the project manager sends the order form and other information to a gatekeeper. In step 106 , a pre-audit is performed. If there is no critical error discovered by the pre-audit, then in step 108 the gatekeeper sends a pre-audit report to the project manager. In step 110 , the project manager reviews the report with the user and others. In step 106 , if there is an error discovered by the pre-audit, then in step 112 , the process is halted to determine if processing is to continue. If the process is halted, then in step 114 , a standard input layout for file transfer is created. If the process is not halted, then in step 116 , the file is returned to the user. In step 118 , files are split for vendors into domestic records 120 and foreign records 122 , which are processed separately. In step 123 , files and an order form are sent to a vendor, who verifies receipt of them. In step 124 , files returned from the vendor are received. In step 126 , when files are returned for foreign records, the project manager receives postal reports from the gatekeeper and prepares a postal summary report. In step 128 , domestic and foreign files are merged into one file with a standard layout for processing. In step 130 , files are processed and a technician sends the project manager files for analysis. In step 132 , an analysis file is created and in step 134 , the project manager send the analysis to the user.
FIG. 2 shows an example method for data cleansing. In step 200 , a qualifying field audit is performed. In step 202 , addresses are standardized, corrected, and ZIP+4-coded. In step 204 , addresses are additionally corrected, and marketing-oriented information is appended. In steps 206 and 208 , addresses are updated with changed information, when appropriate. In step 210 , new addresses are re-processed to verify corrections and add categorization data. In step 212 , output is edited to a single best address for each parsed data element along with selected postal codes and the original address. In step 214 , the best address is matched to a business information database and, based on appended codes, additional corrections are made available. In step 216 , a layout data dictionary with suggestions for leveraging postal data is generated. In general, the example method includes processing domestic addresses including data discovery, postal pre-processing, and, optionally, matching.
Data discovery begins with the pre-audit and includes parsing and reformatting a customer file and verifying that a large number, such as 85% of the records in the customer file have enough address elements to be helped by postal pre-processing. It is verified that there is one address per record. Variations of an address on a single record, i.e., a bill-to and a ship-to, or a street address and a P.O. Box, need to be “exploded” into separate records to be helped by postal processing. It is verified that the data is for the United States only. Different processes are used for foreign data. The pre-audit also includes examining the contents of every field in every record, and a report is produced, which applies letter grades to each data element, reflecting completeness and relevance.
In step 202 , postal pre-processing is performed through a combination of processes and matching to multiple USPS-compiled database, such as a database totaling over 280 million domestic records, for corrections. Standardization, correction, and ZIP+4 coding (a/k/a Coding Accuracy Support System, CASS™, processing) are performed for all domestic addresses, business or consumer.
In step 204 , postal pre-processing in this method also includes applying a file to correct records and append codes, such as “good address, but vacant for the last 90 days” and score each record for accuracy and deliverability. One example file is a second generation delivery sequence file (DSF2). The DSF2 is a file containing substantially all valid addresses serviced by the Postal Service. This comprehensive system enables the substantial elimination of undeliverable addresses, allows mailers to obtain additional postage discounts, and provides valuable information about the make-up of addresses on files. The DSF2 is updated monthly with transactions supplied by the USPS and has 156 million address records for nearly every deliverable address in the United States.
In step 206 , postal pre-processing also includes utilizing address standardization and DSF2 corrections to match to another file, such as the Locatable Address Conversion System (LACS) file. LACS is a file made available by the United States Postal Service (USPS) that provides access to new, changed addresses for locations that have not moved. The LACS has about 5 million records. The vendor receives monthly updates to the USPS LACS file.
Using data that has already been standardized and corrected increases the match rate to the LACS file. The LACS file has addresses changed by the United States Postal Service (USPS) either when a community chooses to provide 911 service, which requires a building number and street address rather than a rural route box location, or when a street name has been changed.
In step 208 , postal pre-processing also includes utilization of corrected and updated addresses from the preceding steps to match to another file, such as the weekly updated 120-million-record National Change of Address (NCOA) file.
The NCOA file is made available by the USPS to provide mailers current change of address information so as to reduce undeliverable mail and increase response rates. This comprehensive system identifies and corrects addressing errors before mail enters the mail stream. A vendor receives updates to the NCOA file every week. NCOA covers four years of moves, with additional possible moves (on near matches to a “from” address) flagged via NCOA-Nixie footnotes. The NCOA has about 120 million records in a rolling four-year database of from- and to-addresses, requiring an almost perfect match to the old name and address to get a new address appended. The NCOA-Nixie flags include a reason code why a new address could not be appended.
In step 210 , new addresses generated from NCOA are then reprocessed: first against LACS and then against DSF2. New addresses coming from LACS that were also not NCOA matches are reprocessed against DSF2.
In step 212 , postal pre-processing results in a set of best address corrections or address updates for each address element. The best address corrections or address updates are appended to the input address, avoiding the creation of a file with multiple and conflicting sets of corrections for each address element as is the common practice from conventional processes.
In step 214 , the results are matched to another file, such as a 31-million-record advanced office system (AOS) file. A certain number of postal processed records have either failed to be recognized by postal processing, or failed to be completely corrected. For instance, records with missing or wrong suite numbers. Historically, matches, at some level of confidence, are made for 30% to 95% of the records that postal processing determines to be uncorrectable. If such a record is matched to a database, (allowing for a lower confidence match is normally acceptable, because it is already known that the client address is incorrect) and if the user agrees the match is valid, the user has the option to further correct the record by using address elements from the matched record in the database.
An example method of data cleansing provides address correcting and updating service for domestic and global address records using a combination of processes. The domestic method includes the following steps: (1) in step 200 , performing a qualifying field audit; (2) in step 202 , standardizing, correcting, and ZIP+4 coding address records via CASS-certified software; (3) in step 204 , correcting and appending marketing information via DSF; (4) in step 206 , updating the address records via USPS LACS; (5) in step 208 , updating the address records via USPS NCOA and NCOA-Nixie flagging of possible moves; (6) in step 210 , applying NCOA for new addresses from LACS, and applying DSF to NCOA addresses, to make certain all addresses have maximum corrections and appended data; (7) in step 212 , editing output to a single best address for each parsed address element, along with selected postal codes, and the address as originally submitted; (8) in step 214 , matching the best address to a domestic business database, and, based on appended codes, making additional corrections on records that match to the database; and (9) in step 216 , providing a layout or data dictionary with suggestions for leveraging postal data. A project manager initiates a field by field audit and a multi-step standardization, correction, and updating process, preferably in three days or less.
Data cleansing includes applying a decision tree to derive a domestic best address. The highest priority is addresses with a positive match to the NCOA file. NCOA-generated addresses are re-processed through address standardization, DSF, and LACS to ensure validity, but are still called NCOA addresses and have an appended move date. An NCOA address, when it is a brand new street, for instance, can be a street name not yet on the DSF file. In such cases the NCOA address stands and is delivered as the best address. The next priority is new addresses gained through LACS that do not match to NCOA. Addresses would be DSF processed on a second pass to validate. The next priority is addresses cleansed through DSF that do not match NCOA or LACS. The next priority is addresses that match address standardization, but not DSF. The last priority is addresses failing to match address standardization. These addresses are parsed and are used to populate the best address fields.
Data cleansing for foreign addresses includes a project manager initiating an audit and then reformatting, correcting, standardizing and appending a single set of best addresses to an original record or records. Preferably, software containing the best available global postal agency information is used.
The global method includes the following steps: (1) performing a qualifying field audit; (2) parsing, reformatting, and correcting city, state/county/prefecture and country names and properly formatting postal codes; (3) applying global postal standardization and correction software; (4) coding output records; (5) appending a single best address for each parsed address element to the address as originally submitted; (6) matching the best address to at least one business database, and, based on appended codes, optionally making additional corrections on records that match to the records in the database. An example of record coding for step (4) is: valid as submitted, corrected, valid after corrections, possibly deliverable; not standardizable or correctable, but appears to have all required address elements for a specific country, possibly because that country does not provide address information that would enable verification/correction, or probably undeliverable, either because two or more critical address elements are missing or because the address has an uncorrectable, pre-unification, German postal code.
Another example method for data cleansing includes receiving a file, such as a flat file on a CD, cartridge, email, etc. An audit is performed on the file to verify that name and address fields are adequately populated. If so, domestic or global processing is performed for postal processing and address correction and standardization. Preferably, the domestic or global processing is performed by a vendor. The result is one best address for a given input address. Then, the best address is matched to a database of business information.
FIG. 3 shows the operation of an example system for data cleansing. In step 300 , the program manager documents user requirements. In steps 302 and 304 , profiles are created based on user-defined requirements. In step 306 , a user input file is received. In step 308 , a pre-audit is performed. In step 310 , a pre-audit report is generated and made available to others, such as by posting to a website. In step 312 , the program manager reviews and sends the report to the user. In step 314 , invalid records are separated and put into a separate file, which will be appended to the valid file received from a vendor in step 328 . In step 316 , an order form and other information is sent to the vendor in a separate file, ahead of the data file. In step 318 , the vendor processes the information. In step 320 , a postal summary report is generated by the vendor and received by the program manager. In step 322 , the program manager reviews the results, creates a summary presentation and shares them with others. In step 324 , the user reviews the results. In step 326 , the file is received from the vendor. In step 328 , the invalid record file (from step 314 ) is combined with the returned vendor file. In step 330 , matching and appending is performed. In step 332 , a results report is generated and made available to others. In step 334 , the program manager generates a project analysis report. In step 336 , the program manager reviews the results and sends them to the user. In step 338 , it is determined whether an investigation is requested for unmatched records. If so, in step 340 , the unmatched records are processed. In step 342 , additional results are made available to the user. In step 344 , the user receives results as they become available.
In general, the example system receives user input addresses, processes them, and provides a file having updated addresses, a postal processing summary report, a match project analysis report, and a pre-audit report. The system is preferably capable of handling about 250,000 records sent monthly by about 400 users. Preferably, the system provides output in 72 hours or less for domestic addresses and 10 days or less for foreign addresses. The system tracks the status of processed data throughout the process. The system sends notifications to the user, e.g., email messages, at various points in the process, such as upon receipt of an input file or when an error occurs. These notification emails are sent to internal and external customers, whenever there is activity on accounts that they are monitoring. Input files may be in any format and may be encrypted or compressed. The system provides a recommended but not required layout to the user. Preferably, users separate domestic and global addresses. Input files may include unique business identifiers, such as DUNS numbers, that correspond to identifiers in the matching databases. An input file is transmittable to the system through the Internet or a leased line. Preferably, batch processes are used to transfer input files.
When the user attempts to login to the system, they are prompted for a user ID and password. Successful login brings the customer to the root of their directory structure. From the root directory the customer has an option to change directories to their puts (deposit files), or their gets (retrieve files) directory.
The example system decompresses the file, if it has been compressed, decrypts the file, if it has been encrypted with PGP, and scans the file for viruses. Then the system sends a file accepted email to the user. The system then pushes the file to an appropriate downstream application and sends a notification of new request email (e.g., file has been submitted) to the user. A downstream application is an internal application to which an inbound file is dispatched, or the internal application from which outbound file processing originates. A viewable status file is selectable by the user. A process to automate file retrieval is also available to the user. Example status files include a filename, profile ID, tracking ID and status code and the like.
The input file is processed to have a predefined record layout, such as the one shown in Table 1 below.
TABLE 1
Example record layout
Start
End
Length
ContactFirstName
1
20
20
ContactMiddleName
21
40
20
ContactLastName
41
60
20
AddressLine1
61
124
64
AddressLine2
125
188
64
AddressLine3
189
252
64
AddressLine4
253
316
64
City
317
380
64
State
381
400
20
PostalCode
401
410
10
CountryName
411
430
20
Business Name
431
550
120
Phone #
551
565
15
DUNS #
566
574
9
Filler
575
584
10
Our Sequence #
585
591
7
Our Sub-sequence #
592
592
1
I′ Indicator
593
593
1
The example system includes a pre-auditor, verifies various aspects of the input addresses, and calculates frequency counts for various fields in the records, such as company name, address 1, address 2, address3, address4, city, state, ZIP and country name. The pre-auditor calculates a number of times one of these fields is repeated, and absence counts, presence counts, number of records and the percentage distinct within each field.
The pre-auditor generates a report including various views of the data, such as all counts, as alphabetical, most frequent content, or alpha characters only.
The pre-auditor generates an all-counts view of the data. For each field in the records, counts are calculated, such as a number of distinct values by field for all records (# of unique values by field), an absence count (number of records missing content for specified field), presence count (number of records populated with content for specified field), number of records (total number of records in the file), percent distinct (percent of distinct values compared to total of records in file (percent=number of distinct values/number of records in the file). The total number of records also equals the total of absence and presence counts. For example, examining the company name field for a file yields the following: the file contains 1,000 records for the company field, 850 records are distinct values, 100 records are absent, and 900 records are present.
The pre-auditor generates an alphabetical view of the data. For each field in the record, the pre-auditor shows a predetermined number, such as 50, of the first occurrences of information within the field sorted alphabetically, preferably in ascending order. For each unique field content, the pre-auditor determines a number count of duplicates, displays the first predetermined number of occurrences by occurrence name, determines the number of duplicates, determines the percentage of occurrences compared to a total number of records in the input file, and determines a number of occurrences for particular fields per the number of total records in the input file. An example is shown in Table 2 below.
TABLE 2
Alphabetical view
Specified Field
Count
Percentage of file that has
(i.e. Company Name)
(Occurrences)
occurrence
Sort alphabetically in
How many times the
Percentage of occurrences
ascending order. Content of
(Company Name) occurs in
compared to total # of
specified field
the file
records in file (% = # of
occurrences/# of total
records in file)
Example:
Example:
Example:
A&A Investment Network
3 (Company Name occurs
0.01% (Company name
Inc DBA Sub
three times in file)
makes up 0.01% of file)
The pre-auditor generates most frequent content view of the data. For each field in the input records, a predetermined number, such as 50, of the highest frequencies or occurrences within the field is determined. For each unique field content, the pre-auditor determines a number of duplicates and displays the first predetermined number of occurrences of most repetitive field content that occurs in the file, giving occurrence name, number of duplicates, and percent of occurrences compared to the total number of records in the file. An example is shown in Table 3 below.
TABLE 3
Most frequent content view
Specified Field
Percentage of file that has
(i.e. Company Name)
Count
occurrence
Content of specified field
Sorted in descending order
Percentage of occurrences
(i.e. Company Names)
according to the highest
compared to total # of
occurrence on the file, how
records in file (% = # of
many times does the
occurrences/# of records in
(Company Name) occur in
file)
the file
Example:
Example:
Example:
Edward A Kaplan DBA
40 (Occurs 40 times in file)
0.12% (This company name
Edward A Kaplan
makes up 0.12% of file)
The pre-auditor generates an alpha characters only view of the data. For each of the fields, the pre-auditor displays a predetermined number, such as 50, of the highest frequencies or occurrences of records containing non-numeric, alpha-numeric characters within a specified field (i.e., A-Z, 1-9 and a blank space). Unacceptable occurrences include more than 1 occurrence of anything other than alpha-numeric characters. For each unique field, content with alphas only includes a count of the number of duplicates, the first predetermined number of occurrences, the occurrence name, the number of duplicates, and the percent of occurrences compared to total number of records in the file. An example is shown in Table 4 below.
TABLE 4
Alpha characters only view
Specified Field
Percentage of file that has
(i.e. Company Name)
Count
occurrence
Content of specified field
Sorted in descending order
Percentage of occurrences
(Company Name)
according to the highest
compared to total # of
occurrence of special or
records in file (% = # of
non-printable characters in
occurrences/# of records in
the file, how many times
file)
does the (Company Name)
occur in the file
Example:
Edward A Kaplan DBA
40 (Occurs 40 times in file)
42.39% (This company
Edward A Kaplan
name makes up 42.39% of
file)
The example system removes any invalid records from the input file and stores them in a new file. An invalid indicator with indicators, such as “I” for invalid or “V” for valid are added to the record. This file is not processed, but rather held until the rest of the input file is processed and then combined with results file and sent to a matching process.
There are various rules for determining invalid records. For example, for domestic records, valid combinations include: address 1 and city and state, address 1 and ZIP, address 2 and city and state, address 2 and ZIP, address 3 and city and state, address 3 and ZIP, address 4 and city and state, address 4 and ZIP. If no street address is present, address — 1, address — 2, address — 3, and address — 4 are checked. If addresses 1, 2, 3 and 4 are blank, the record is ineligible. The record is ineligible if address — 1, address — 2, address — 3 or address — 4 is present, but there is no ZIP code or city/state combination. For domestic records, invalid combinations include: no address present, address 1 and city (no ZIP, no state), address 2 and city (no ZIP, no state), address 3 and city (no ZIP, no state), address 4 and city (no ZIP, no state), address 1 and state (no ZIP, no city), address 2 and state (no ZIP, no city), address 3 and state (no ZIP, no city), and address 4 and state (no ZIP, no city).
The example system includes a vendor order form processor. In an example manual process, a program manager completes an order form for each input file. In an example automated system, the information on the order form is provided to a technician, who verifies the information. This information is sent to a vendor in a control file and is received prior to the data file. Both vendors use the same control file layout. This information is also used to send a vendor postal summary report to the program and to generate a bill for files processed.
The example system includes an example user interface including a template of the information sent to the vendors. The program manager and customer define profile needs and order form information. A profile is a set of characteristics and specifications for customer file transfers as defined by administrator entries into the user's account through an administrative interface. An administrative interface is a user interface for accessing a system for viewing, monitoring, and managing user accounts and profiles. The order form is automatically captured and electronically communicated to the vendors. An example order form is shown in Table 5 below.
TABLE 5
Example order form
Read
Field Name
Required?
Only?
Source
Contract ID (free form)
Y
Program Manager
Our Contact Name
Y
Program Manager
Our Phone
Y
Program Manager
Our Email
Y
Program Manager
File Quantity
Y
Calculated (based on
initial number of
records from BDE)
Multiple File indicator
Y
Program Manager
Vendor Needs: (Only
Y
Defaults are:
DSI will be using this
Maintain Diacritics =
data but it will appear
No
on Axiom's)
Reject USA Records =
Maintain Diacritics
Yes
Reject USA Records
Canadian NCOA = No
Canadian NCOA
The example system includes a file transfer protocol (FTP) program. Files are sent to the vendor upon receipt. Preferably, the files arrive individually in order for the vendors to process the post summary report for each job and send the post summary report to the program manager. Bundling multiple files is also an option.
The example system including completing the pre-audit, creation of a control file, and creation of an input file for each vendor. An example layout of the input file is shown in Table 6 below.
TABLE 6
Example layout of input file
Start
End
Length
ContactFirstName
1
20
20
ContactMiddleName
21
40
20
ContactLastName
41
60
20
AddressLine1
61
124
64
AddressLine2
125
188
64
AddressLine3
189
252
64
AddressLine4
253
316
64
City
317
380
64
State
381
400
20
PostalCode
401
410
10
CountryName
411
430
20
Business Name
431
550
120
Phone #
551
565
15
DUNS #
566
574
9
Filler
575
584
10
Our Sequence #
585
591
7
Our Sub-sequence #
592
592
1
I′ Indicator
593
593
1
The example system includes a vendor output file receiver. The output file receiver sends a notification of receipt.
The example system includes a vendor-to-user linker. An incoming file from a user is linked to a vendor. When an output file is received from the vendor, the linker returns the output file to the user. Vendor files are combined with the invalid record file from the pre-audit process. This file includes raw user input data and postal pre-processed data or the user data and no postal pre-processed data for invalid records. The valid and invalid records are combined and a single file is sent to the matcher.
The example system includes a matcher. The following fields are mapped: the original company name from the user, address from the vendors, and original phone number from the user. If the addresses are blank, then the original user address is used. If address information from a vendor is blank, then the matcher matches against the original customer address information.
The example system includes a project creator. A match technician creates a new project, renames an output file and uses new or original customer address information to perform matching. Users send a second file using a different profile in a batch file. A file is received from a vendor and matching is performed per profile instructions. Resulting matched records are sent to an appended file in the example system and unmatched records are sent to an investigator in the example system, if requested by the user.
The example system includes external interfaces. Files are sent and received from vendors. The system sends the original customer address to a vendor. The vendor sends the best corrected address back along with the original customer address and postal code information. Preferably, standard input and output layouts are used.
FIG. 4 shows an example vendor domestic address cleansing system that standardizes addresses according to USPS specifications. In step 400 , a source file is posted to an FTP site 402 , address cleansing is performed 404 , DSF and LACS processing is performed 406 , and NCOA processing is performed 408 , and addresses are reformatted and components are selected 410 .
The system enhances the user's data by verifying and correcting 5-digit ZIP codes, applying ZIP+4, delivery point barcodes, carrier route codes, and line of travel data. The system also ensures a CASS-certified output. CASS is the USPS certification process for address standardization products, which is updated and re-certified annually.
The vendor address cleansing system has a reformat address component selection. This component reformats output records to comply with the standard output layout. The process also ensures that the optimum address components are selected from DSF/LACS/NCOA based on priorities set by the vendor.
FIG. 5 shows an example vendor international hygiene system. In step 500 , conversion is performed to review data, correct initial problems, and correct problems discovered in a first pass of phase one. In step 502 , phase one is performed, including country isolation and name standardization, postal code isolation and reformatting, state or province isolation, review of rejects and possibly rerun the conversion. In step 504 , filters are applied for obscenity detection and miscellaneous garbage detection. In step 506 , domestic records are split off. In step 508 , phase two is performed, including postal code validation and correction, city validation and correction, and street validation and correction, where available. Instep 510 , Canadian NCOA is performed, if requested.
The present invention has many advantages. For first class mailers, the user's mail, such as invoices, is forwarded to new addresses when the addressees move, but having the new address in advance saves one to two weeks of delivery time. For standard class (bulk) promotions, more pieces are delivered with more accurate addresses yielding a higher response rate. For all businesses, data cleansing facilitates internal data integration efforts and generates high match rates to other data. Cost savings are realized, depending on the size of the customer list. The present invention is able to determine a correct address and match it to a unique business identifier in a database for up to 95% of the addresses determined to be uncorrectable by the U.S. Postal Service. The present invention has a database with nearly 19 million marketable U.S. business records and 14 million more in an historical repository. The present invention appends data that is about 98% ZIP+4-coded due to monthly address updating and maintenance routines. For international addresses there are about 41 million marketable records. The matcher may provide an improved address even when postal correction software is unable to.
It is to be understood that the above description is intended to be illustrative and not restrictive. Many other embodiments will be apparent to those of skill in the art upon reviewing the above description, including other systems and methods for data cleansing and other similar differences. The present invention applies to many fields where data is cleansed. Therefore, the scope of the present invention should be determined with reference to the appended claims, along with the full scope of equivalents to which such claims are entitled. | There is provided a method that includes (a) receiving an input postal address, (b) comparing the input postal address to a standard, (c) providing a single best postal address corresponding to the input postal address based on the comparing, (d) matching the single best postal address to a business in a business information database, (e) obtaining a business address for the business from the business information database, and (f) correcting the single best postal address, based on the business address, to yield a corrected postal address. There is also provided a system that performs the method, and a machine-readable medium having instructions stored thereon that cause the machine to perform the method. | 8 |
BACKGROUND OF THE INVENTION
Kosaka et al U.S. Pat. No. 4,088,450 discloses a plurality of catalysts arranged in a desirable order based on the temperature gradient existing in the chamber for reaction. The operating temperature of the catalysts and the temperature of the portion of the reaction chamber it is in, are matched so as to avoid a catalytic degradation and/or catalytic inactivity.
Peterson et al U.S. Pat. No. 4,282,835 provides for synthesizing CO and H 2 fuel from methanol and water in a second synthesizer. The methanol is confined in an alcohol tank as a liquid. The water is confined in a water tank. A fuel pump and a water pump force fuel and water to a mixing valve. A heat exchanger heats the fuel and water to a gas which passes through nickel on alumina catalyst at 500° C. where the methanol dissociates to CO+H 2 . The gas passes to a second synthesizer containing Fe on Alumina catalyst above 500° C. where water and carbon monoxide form hydrogen and carbon dioxide. The gas is then mixed with air and passes to the engine.
SUMMARY OF THE INVENTION
A reactor apparatus comprising
a reaction chamber wall, a reactor chamber inlet means, a reaction chamber outlet means,
an inner fins, and
catalyst bed material;
said reaction chamber wall enclosing said catalyst bed material, and defining a reaction chamber therewithin;
said inner fins being attached to said reaction chamber wall and extending therefrom into said reaction chamber;
said inlet means and said outlet means each being connected to said reaction chamber wall.
A method of fuel treatment and distribution for an internal combustion engine comprising the sequence of steps as follows:
(a) heating a catalyst bed reactor to a start-up temperature using exhaust gas from an internal combustion engine being operated on atomized alcohol; said catalyst bed reactor comprising a partial combustion catalyst and a methanol dissociation catalyst;
(b) vaporizing liquid alcohol to form alcohol vapor;
(c) mixing said alcohol vapor with air to form a partial combustion mixture;
(d) contacting said partial combustion mixture and said partial combustion catalyst whereby a dissociation mixture is formed and heat is evolved;
(e) contacting said dissociation mixture and said dissociation catalyst to form a hydrogen-rich fuel;
(f) mixing air and said hydrogen rich fuel to form a total combustion mixture;
(g) burning said total combustion mixture in an internal combustion engine.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a cross-sectional view of a reactor in accordance with the present invention.
FIG. 2 is a longitudinal cross-sectional view of a reactor in accordance with the present invention.
FIG. 3 is a schematic flow diagram of an automobile fuel system in accordance with the present invention.
DETAILED DESCRIPTION OF THE INVENTION
With more particular reference to the drawings, it is seen in FIG. 1 that a reaction chamber 10 is supported within the reactor 3 by supports 16 and/or by springs 14 and 14'. The reactor chamber wall 10 encloses the catalyst bed material 11. Inner fins 9 extend from the reaction chamber wall 10 to which they are attached. The inner fins extend from the reaction chamber wall inwardly into the reaction chamber defined by the reaction chamber wall. Outer fins 13 are connected to the reaction chamber wall 10. Outer fins 13 extend outwardly from the reaction chamber wall 10 into the heat exchange chamber 12. The heat exchange chamber 12 is defined by the inner surface of the heat exchange wall 17 and the outer surface of the reaction chamber wall 10.
As shown in FIG. 2, the heat exchange wall 17 encloses the reaction chamber wall 10. The supporting spring means 14 and 14' are connected to the inner surface of the heat exchange wall 17 and the outer surface of the reaction chamber wall 10.
As shown in FIG. 3, the reactor 3 is connected by conduit 19 to a super-heater 5. The superheater 5 receives vapor phase alcohol from the vaporizer 2 through line 20. Air is pumped through line 15 from compressor 21 into line 20. The mixture of air and methanol vapor passes through line 20 to the superheater 5. Alcohol from the alcohol tank 1 is pumped through line 22 by pump 23 to the vaporizer 2. Valve 24 in line 22 is provided to limit the flow of liquid alcohol to the vaporizer 2 from the alcohol tank 1. The mixture of air and alcohol vapor passes through line 19 into the reactor 3. The reactor 3 is heated by exhaust gas from the engine 4. The exhaust gas passes through line 25 to the reactor 3. The line 25 has valve 26 therein to limit the flow of exhaust gas to the reactor 3. Exhaust gas leaves the reactor 3 through line 27. The vaporizer 2 is provided with a line 29 through which hot engine coolant is passed from the engine to the vaporizer 2. Engine coolant passes from the vaporizer 2 through line 30. Line 30 is connected to engine 4. The filter 6 is connected to the reactor 3 by line 31. The filter 6 removes solids from the hydrogen rich gaseous mixture passing therethrough. The filter 6 is connected by line 32 to the engine 4. Valve 36 in line 32 is provided to limit the flow of the hydrogen rich gaseous fuels in the engine. The valves 24 and 36 completely block the dissociation system including vaporizer to the filter when the system is not in operation. Line 8 is connected to the line 33. Line 33 is connected to the engine 4. Hydrogen rich gas in line 32 mixes with air from line 8 in the line 33. Liquid alcohol passes through line 7 to line 33. The valve 34 in line 7 limits the flow of liquid alcohol therethrough. The liquid alcohol passing through line 7 is atomized prior to being fed to the engine 4.
The preferred alcohol for use as the alcohol fuel in the alcohol tank 1 is methanol.
The fins 9 and 13 extend the length of the reaction chamber wall. Both the inner fins 9 and the outer fins 13 serve to distribute heat along the reaction chamber wall. Inner fins 9 serve to distribute heat into the reactor bed 11 from the reaction chamber wall 10. The outer fins 13 serve to transfer heat from the heat exchange chamber 12 into the reaction chamber wall 10.
The ends of reaction chamber wall 10 are preferably covered by a screen or wire mesh (not shown) to retain the catalyst bed 11 therein.
The engine is started by methods known in the art for starting internal engines for example by use of an alternate fuel such as liquid methanol delivered through line 7 or a gaseous fuel like propane. After starting the engine, the hot exhaust gases heat the reactor 3 by passing through the heat exchange chamber 12. The outer fins 13 conduct heat from those hot exhaust gases and transmit it to the reaction chamber wall 10. The fins 9 transfer heat from the reaction chamber wall 10 into the reaction bed 11. When the initial operating temperature is reached, the mixture of air and methanol vapor are fed to the reactor. Preferably the reactor contains a dual catalyst bed. The initial catalyst contacted by the mixture of air and methanol vapor being a partial oxidation catalyst for example copper/nickel. The subsequent catalyst contacted by the alcohol and partial combustion product mixture being a dissociation catalyst such as copper/zinc catalyst. Partial combustion occurs between the methanol and the air in the initial stage of the reactor 18. This partial combustion produces heat. The heat produced in the initial stage of the reactor 3 is transferred to the subsequent stage by the inner fins 9.
Once the catalyst bed is preheated to the initial reaction temperature by the engine exhaust gas, valve 26 is closed and valves 24, 35 and 36 are opened by temperature switch. Valve 28 is line 38 is first opened to send hot exhaust gas to the superheater 5 before closing valve 26. The reaction temperature within the reactor 3 is maintained by the rate of partial combustion. The rate of partial combustion is controlled by the amount of air injected through line 15 by control of valve 35. Valve 35 is temperature responsive to the outlet gas temperature in line 31. Valve 35 is connected to line 31 by temperature control signal. The temperature control in line 31 is not shown. Valve 35 is also connected to line 22 by flow rate sensor signal. The flow rate sensor signal sets the maximum opening of valve 35 at the measured alcohol flow rate. The temperature control signal reduces the opening of valve 35 to lower the air flow rate from the maximum if the temperature is over the specified upper limit of the product gas temperature. This air flow control may be done by microprocessor which is not shown in FIG. 3.
During cold start up exhaust from the engine passes into the heat exchange chamber of reactor 3 through line 25 and valve 26. The exhaust leaves the heat exchange chamber through line 27. While the reactor is being heated up to the operational temperature, valve 28 in line 38 is closed so that exhaust from line 37 passes into line 25 and into the heat exchange chamber of the reactor 3. The exhaust gas leaving the reactor 3 through line 27 enters the superheater 5 through line 39 and leave the superheater through lines 40 and 74 to vent. Valve 44 in line 45 is closed during this period. During this period the vaporizer 2 is heated with engine coolant. When the reactor has reached its operating temperature, valve 28 in line 38 is opened by a temperature switch so that exhaust no longer passes from line 37 into line 25 but rather the exhaust from line 37 is channelled into line 39. The valve 26 is then closed. Thus, the reactor 3 is isolated from exhaust heat and adiabatic dissociation begins in the reactor. The valve 44 controls the exhaust gas flow to the superheater 5 to give the temperature of the methanol vapor from the superheater 5 at the specified inlet temperature for the adiabatic reactor 3. The vaporizer 2 is optional. Thus, liquid methanol may be fed directly into the superheater 5 from the methanol or alcohol storage tank 1. Alternatively engine exhaust may be passed from the output line 40 of the superheater 5 into the feedline 29 of the vaporizer 2. In which case, engine coolant would not be fed into the feedline 29 of vaporizer 2.
The air being fed through line 15 may be preheated by preheater 41. The preheater 41 may be fed exhaust from line 37 to provide the preheating heat for air being fed through line 15 into line 20. Beneficially the preheated air does not lower the temperature of the liquid alcohol and/or alcohol vapor being fed to the superheater 5 through line 20.
The reactor 3 preferably is provided with insulation over the heat exchange wall 17 to maintain the temperature therewith and minimize the transfer of heat therefrom. As an alternative to valve 26, a restricting orifice may be provided. During cold start hot exhaust gas flows through the orifice to the reactor to preheat the catalyst bed in reactor 3 to operating temperature by closing the valve 28 in line 38. When the reactor 3 is in operation, the orifice allows only a portion of hot exhaust gas to flow to the reactor 3 with the balance of the exhaust gas flowing through line 38 by opening the valve 28. In this manner, the heat loss from the reactor 3 can be minimized and some heat recovery from the exhaust gas may be realized in the reactor.
The principal function of exhaust within the heat exchange chamber of the reactor 3 is to initially heat up the reactor 3 and then to sustain heat losses to the atmosphere to maintain the temperature of the reaction chamber 11 free from heat loss to the atmosphere. After the initial heat up of the reactor 3 to the operating temperature, a major portion of the exhaust in line 37 may be passed to the vaporizer and/or superheater. Thus only a small portion of the exhaust would be required to make up for heat losses from reactor 3 to the surrounding atmosphere. It is within the scope of the invention to completely block the flow of exhaust to the reactor 3 after it initially reaches operating temperature. In this case the heat losses to the atmosphere would be made up by the additional partial combustion of methanol.
Physical Configuration and Functions of Reactor Components
FIGS. 1 and 2 show the schematics of reactor 3. The reactor has two divided sections: the inner section holding the catalyst bed and the surrounding empty chamber. The reaction chamber wall 10, separating the catalyst bed 11 and the heat exchange chamber 12, has inside fins 9 and outside fins 13. During cold starts the hot engine exhaust gas flows through the heat exchange chamber to provide the heat required for preheating the bed to a desired temperature. The fins on the reaction chamber wall will enhance the heat transfer and, thus, reduce the preheating time. During normal dissociation operation, the heat exchange chamber is isolated from the exhaust gas flow and, thus, acts as insulation. The feed to reactor 3 is a mixture of superheated methanol and air. For thermally neutral conversion of methanol, the air/methanol ratio in the feed and the reactor inlet temperature are controlled.
The fins inside and outside of the reaction chamber wall are placed parallel to the flow directions of the reactants in the bed and of the exhaust gas in the heat exchange chamber, respectively, in order to minimize the pressure drops in both flows.
The inside fins on the reaction chamber wall have important functions for maintaining catalyst activity and physical integrity. During adiabatic operation the fins will help to maintain a more even temperature distribution in the bed by facilitating longitudinal heat transfer. This heat transfer effect is beneficial to the maintenance of the catalyst activity by reducing the peak temperature generated by the reaction between methanol and oxygen in the front partial combustion zone of the catalyst bed, since a higher temperature deactivates catalyst more by sintering. Further, the inside fins may be beneficial for catalyst pellet integrity by restricting pellet motion resulting from sudden changes in car speed or car vibrations due to rough road conditions.
As shown in FIG. 2, springs 14 and 14' or some other mechanical means of dampening motion may be installed in the heat exchange chamber to absorb any abrupt movements of the automobile without detrimentally affecting catalyst physical integrity.
Because a rapid preheating of the catalyst bed by heat exchanger is required during cold starts, a reaction chamber wall shape that gives a larger heat transfer area is preferred at the same catalyst volume. For this reason the reaction chamber wall also has many inside fins 9 and outside fins 13. FIGS. 1 and 2 show a configuration of the reactor. FIG. 1 shows that the reaction chamber wall in the reactor has a large width-to-depth ratio in order to have a large peripheral surface area at the same volume.
Since the reactor must fit into the available space in an automobile, the reactor size and shape must correspond to that space.
Overall Fuel System
FIG. 3 shows a schematic flow diagram of the automobile fuel system of the invention. Major components of the fuel system are a vaporizer 2, a superheater 5, a filter 6, and by-pass line 7 in addition to the reactor.
In the vaporizer 2 the engine coolant, normally at 200°-220° F., provides the heat for the methanol vaporization. In the superheater, the methanol temperature is raised to the desired reactor inlet temperature by heat exchange with the exhaust gas. The vaporizer 2 is optional because the superheater may be used for the methanol vaporization and superheating by directly feeding liquid methanol into it. Air is injected through line 15 to the alcohol feed stream normally before the superheater in order to allow enough time for mixing of the air and alcohol prior to the reactor. The filter 6 collects fines from the catalyst bed.
The by-pass line 7 delivers liquid alcohol directly to the engine as required during cold start or high load driving (acceleration or high speed driving). During cold start, the engine 4 must run on liquid or vaporized alcohol until the dissociation reactor completes its start-up phase. During high load driving the fuel requirement in excess of the maximum throughput of the reactor is provided with liquid alcohol from tank 1 delivered through the by-pass line 7.
The direct feeding of liquid alcohol in excess of the maximum throughput of the reactor may be beneficial for overall car performance without significantly reducing the benefits of the dissociation. The liquid alcohol fed to the engine will boost the engine power by increasing the energy density of the combined fuel when the power is needed at high load conditions. Further, it may lower the NO x emissions by reducing the combustion temperature in the engine.
The preferred operating mode for the dissociated methanol engine is to operate for maximum efficiency at low-load driving conditions, and for maximum performance at high-load transient driving conditions. Low-load operation consisting of idle and constant speed driving does not require a high power output from the engine. For low-power output, the engine can be operated at a maximum air-fuel ratio or a minimum equivalence ratio to give maximum efficiency. With dissociated methanol the equivalent ratio can be reduced as low as 0.3 without hampering smooth engine operation due to its high hydrogen content. For maximum power output, methanol in excess of the reactor throughput can be by-passed and fed directly into the engine. Air flow is unthrottled. The result is an increase in fuel density up to an equivalent ratio of 1.0, which gives maximum power output.
Operation can be accomplished with a driver controlled accelerator that sends a signal to a microprocessor, which in turn monitors and adjusts engine performance as necessary. The micro-processor is not shown in FIG. 3. Adjustments such as spark advance, air-fuel ratio, etc. are made. The micro-processor maintains the required air-fuel ratio during low-load driving demand by throttling the air flow to the engine. During high-load transient demands, such as acceleration to cruise speed and hill climbing is required, additional fuel as liquid methanol is injected by opening by-pass valve 34. In this mode, air-fuel ratio varies as fuel density is adjusted to give the required engine power output and hence good driving performance.
EXAMPLE
Cold Starts
Since the cold start of the reactor requires hot engine exhaust gas for preheating of the catalyst bed the engine 4 must be turned on by a method independent of the methanol conversion system. During this period of the engine may run on liquid alcohol delivered through the by-pass line.
Once the catalyst bed temperature in the reactor has risen to the initial operating temperature, superheated alcohol is fed to the reactor with air injection through line 15. Because of the exothermic heat generated by partial combustion of alcohol, the catalyst bed temperature will further rise until endothermic alcohol dissociation becomes effective.
For a 20/10 Cu/Ni catalyst on silica the bed temperature for initiating the partial combustion reaction for methanol is about 300° F. or above. A lower temperature is acceptable if a more active catalyst is used.
The engine can be started independently with a gaseous start-up fuel such as propane, electrically vaporized methanol or finely atomized methanol.
Adiabatic Alcohol Conversion
Once the cold start phase of the reactor is completed, the reactor is operated adiabatically with air injection rate controlled at a fixed O 2 /methanol molar ratio in the feed for thermally neutral, adiabatic conversion. The O 2 /methanol feed ratio is normally 0.16 for the adiabatic conversion. The ratio is less than the theoretical number of 0.174 because of the exothermic formation of such by-products as methane and dimethyl ether in very small quantities. When the methanol conversion goes to completion at the air injection rate and there are no heat loss from reactor to surroundings, the product gas temperature is the same as the feed temperature.
With a dual catalyst bed of Cu/Ni and Cu/Zn catalysts, the following three reactions take place as major reactions
CH.sub.3 OH(g)+1/2O.sub.2 →H.sub.2 +CO+H.sub.2 OΔH.sub.298 =-36,134 cal (I)
CH.sub.3 OH(g)→2H.sub.2 +COΔH.sub.298 =21,664 cal (II)
H.sub.2 O(g)+CO→H.sub.2 +CO.sub.2 ΔH.sub.298 =-9,838 cal (III)
Methanol is first converted via Reactions (I) and (II) in the Cu/Ni catalyst zone and the remaining methanol is converted via Reactions (II) and (III) in the following Cu/Zn catalyst zone. Because Reaction (I) is very fast on a Cu/Ni catalyst, oxygen is rapidly consumed to completion in the zone. The rapid progress of Reaction (I) creates a temperature peak in the zone. After the depletion of oxygen the endothermic reaction (Reaction (II)) becomes dominant and, thus, cools down the bed temperature. The gas leaving the reactor is very close to equilibrium for the water/gas shift reaction because of the excellent shift activity of the Cu/Zn catalyst.
Having thus described the invention by reference to certain of its preferred embodiments it is respectfully pointed out that embodiments described are illustrative rather than limiting in nature and that many variations and modifications are possible within the scope of the present invention. Such variations and modifications may appear obvious and desirable to those skilled in the art upon a review of the foregoing description of preferred embodiments. | A method of methyl alcohol treatment and distribution for an automobile internal combustion engine including the sequence of steps as follows:
(a) heating a catalyst bed reactor to a start-up temperature using exhaust gas from an internal combustion engine being operated on atomized methyl alcohol; the catalyst bed reactor including a partial combustion catalyst and a methanol dissociation catalyst;
(b) isolating the catalyst bed reactor from the exhaust;
(c) vaporizing liquid methyl alcohol to form alcohol vapor;
(d) mixing the alcohol vapor with air in a constant ratio of oxygen to alcohol at variable alcohol flow rates, to form a partial combustion mixture;
(e) contacting the partial combustion mixture and the partial combustion catalyst to exothermically form dissociation mixtures the dissociation mixture including methanol vapor, water vapor, carbon monoxide, and hydrogen each in substantial proportion;
(f) contacting the dissociation mixture and the dissociation catalyst to endothermically form hydrogen-rich fuel the hydrogen-rich fuel including hydrogen and carbon monoxide each in substantial proportion, the hydrogen rich fuel being formed from the alcohol vapor substantially adiabatically;
(g) mixing air and the hydrogen-rich fuel to form a total combustion mixture;
(h) burning the total combustion mixture in an internal combustion engine. | 8 |
CROSS-REFERENCES TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. application Ser. No. 09/567,250, filed May 9, 2000, which is hereby incorporated herein by reference in its entirety, and which is a continuation of Ser. No. 09/193,459, filed Nov. 16, 1998, which claimed the benefit of U.S. application Ser. No. 60/088,149, filed Jun. 5, 1998.
STATEMENT AS TO ANY INVENTION RIGHTS UNDER FEDERALLY SPONSORED RESEARCH
[0002] Not applicable.
BACKGROUND OF THE INVENTION
[0003] The present invention relates generally to the field of advertising systems, and more particularly to the field of Internet advertising.
[0004] The worldwide network of computers connected through the Transmission Control Protocol/Internet Protocol (TCP/IP) communications standard, commonly known as the Internet, has seen explosive growth during the last several years. This growth has been fueled in part by the introduction and widespread use of so-called “web” browsers, which allow for simple graphical user interface (GUI) access to network servers, which support documents formatted as so-called web pages. The World Wide Web (WWW), or “web”, is a collection of servers on the Internet that utilize a Hypertext Transfer Protocol (HTTP), which is an application protocol that provides users access to files (which can be in different formats such as text, graphics, images, sound, video, etc.) using a Standard Generalized Markup Language (SGML), which is an information management standard for providing platform-independent and application-independent documents that retain formatting, indexing, and linking information. SGML provides a grammar-like mechanism for users to define the structure of their documents and the tags they will use to denote the structure in individual documents. The page description language known as Hypertext Markup Language (HTML) is an application of SGML. HTML provides basic document formatting of text and images and allows the developer to specify hyperlinks, or “links,” to other servers and files. Use of an HTML-compliant client, such as a web browser, involves specification of an address via a Uniform Resource Locator (URL). Upon such specification, the client makes a TCP/IP request to the server identified in the URL and receives a “web page” (namely, a document formatted according to HTML) in return.
[0005] Electronic mail (E-mail) is another important part of online activity. Conventional e-mail is the exchange of text messages and computer files over a communications network, such as a local area network or the Internet, usually between computers or terminals. Routing of e-mail on the Internet is typically accomplished through the use of a protocol for sending messages called the simple mail transfer protocol (SMTP). Multipurpose Internet mail extensions (MIME) extend SMTP to permit data, such as video, sound, and binary files, to be transmitted by Internet e-mail without having to be translated by the e-mail client into ASCII format. This is accomplished by the use of MIME types, which describe the contents of a document. A MIME-compliant client application sending a file, such as one of various conventional e-mail programs, assigns a MIME type to the file. The receiving application, which must also be MIME-compliant, refers to a standardized list of documents that are organized into MIME types and subtypes to interpret the content of the file. MIME is part of HTTP, and both web browsers and HTTP servers use MIME to interpret e-mail files they send and receive. Post Office Protocol 3 (POP3) is a recent version of a standard protocol for receiving e-mail. POP3 is a client-server protocol in which e-mail is received and held in a mailbox for a user by a network server. Periodically, the end user checks the mailbox on the network server and downloads any e-mail. An alternative protocol is Interactive Mail Access Protocol (IMAP), according to which a user views e-mail at the server as though it was on the user's computer, and an e-mail message deleted locally is still on the server. Thus, POP3 can be thought of as a “store-and-forward” service, while IMAP can be thought of as a remote file server. Therefore, an e-mail message is typically sent with SMTP, and after a network server receives the e-mail message on the end user recipient's behalf, the e-mail message is typically read by the end user using POP3 or IMAP.
[0006] In addition to older basic e-mail systems, including basic ASCII e-mail clients using SMTP and POP3, some enhanced e-mail clients, such as Eudora Pro Email v. 4.0, display HTML portions of messages according to HTML formatting contained in the e-mail message bodies. Also, web-based e-mail systems, such as are currently offered by Hotmail™ and Yahoo™, are accessible through web browsers. In those systems, e-mail messages are formatted into web pages, or portions thereof, for formatted viewing control through web browsers. Thus, plain text e-mail messages received by those web based e-mail systems are converted into web pages for viewing by web browsers.
[0007] Shared public message networks include Usenet Newsgroups, Internet Relay Chat, Fidonet, RIME, ELINK, and a host of others. Public message networks also include public message areas in proprietary online systems. Most are normally set up according to separate general interest categories (e.g., “conferences,” “forums,” or “newsgroups”), subjects within those categories (e.g., “subjects,” “topics,” or “threads”), and finally individual messages or postings within each subject, typically arranged chronologically, as well as according to earlier messages to which they respond. Also included in this category of public messaging are instant messaging programs, which allow users to communicate publically with other users in real time. These conferences typically are carried by many online systems regionally, around the country, or even around the world. Newsgroups also have an Internet protocol which governs their transmission called network news transfer protocol (NNTP). As with e-mail clients, public messages are also accessible through web browsers, enhanced public messaging clients capable of displaying HTML formatting, and basic ASCII clients.
[0008] The recent growth of information applications on international public packet-switched computer networks, such as the Internet, suggests that public computer networks have the potential to establish a new kind of open marketplace for goods and services. As web pages, discussion forums and e-mail communications are used more nationally and internationally, it is highly desired that manufacturers and merchants be able to non-offensively advertise their goods and services to users during their regular course of Internet activity. With only limited success, such advertising has been done through the use of images as well as text transferred over the Internet. Advertisements transferred over the Internet often, but not always, make use of trademarks. A “trademark” is a word, design, color, sound, smell, etc., or any combination thereof, used by a manufacturer or merchant to identify their goods and/or services and distinguish them from others. In general, advertisements include most types of communications promoting goods and/or services of organizations or individuals, as well as promoting the organizations or individuals themselves. Entities with access to potential viewers of advertisements often charge a fee to other entities interested in advertising themselves and/or their goods and/or services.
[0009] On the Internet, as in more traditional venues of advertising, such as billboards, TV commercials, products, etc., most advertisements (ads) include promotional material intended to be used to interest consumers with particular goods or services. Currently, one primary way to advertise on the Internet is through ad banners, which often contain static or animated images, with or without trademarks, and normally advantageously function as hyperlinks to advertisement owner web pages. Unfortunately, banner ads often disappear with scrolling by the user and take up precious screen space. Furthermore, because of typically large graphical content, banner advertisements are often slow in downloading. As a result, users often move down a web page or to another web page and do not wait for advertisements to complete the downloading process if text or other content is displayed before, or simultaneously with, the advertisements, thereby clearly diminishing the impact of the advertisements. If text or other content is displayed only after an advertisement is completely downloaded, users may become very frustrated with the owner of the advertisement if the wait time is prolonged. Interstitial displays, such as splash screens which appear in between web page requests and before a web page is actually delivered, also provide advertisement opportunities, but they are often extremely brief, thereby greatly lessening their effect.
[0010] Others have addressed the problem of getting advertisements to an end user through the use of screensavers, such as a product commercialized by PointCast, Inc., Sunnyvale, Calif., as described in U.S. Pat. No. 5,740,549 to Reilly, et al. Although the screensaver program approach does appear to be capable of communicating advertisements to some users, there are clearly disadvantages to displaying these advertisements in an area outside of the normal user work area during times of inactivity when a user may typically not be looking at the display. In addition, the extra steps required to install and update such software can be too complicated or cumbersome for some users. Advertisers also have used broadcast e-mails and public postings to send advertisement messages from themselves containing plain text, as well as HTML formatting for more effective display. In general, e-mail messages and public postings containing hyperlinks pointing to additional information are also known, such as described in U.S. Pat. No. 5,790,793. Unfortunately, users often immediately delete unsolicited e-mail messages, as well as those sent from unknown senders.
[0011] Outside the Internet, top of mind awareness (TOMA) advertising acquaints the public with advertisers' brand-names, logos, trademarks, etc., through selective infiltration and saturation in the market. The purpose of such advertising is not to compel immediate purchase, but to enhance public awareness of the availability of the product from a particular manufacturer or merchant, so that when shoppers are at the retail markets to make purchases, they will recognize brands and immediately have higher perceived values of those products in relation to like products by other manufacturers or merchants. The key to a TOMA campaign is repetition since the more times that an individual is exposed to a particular brand-name, logo, trademark, etc., the more likely that individual will buy a particular product when making a buying decision in the future. Unfortunately, on the Internet, TOMA advertising is rarely accomplished successfully since, as discussed above, most conventional Internet advertising methods often result in very limited exposure to users. This conclusion is evidenced by the attention brokerage system described in U.S. Pat. No. 5,794,210, which actually teaches a method of compensating users for paying attention to advertisements on the Internet.
[0012] There is, therefore, a need for an advertising system for addressing these and other needs and problems.
BRIEF SUMMARY OF THE INVENTION
[0013] An advertisement system and method are provided for inserting into an end user communication message a background reference to an advertisement. In some preferred embodiments of the present invention, the background reference causes an advertisement image to be tiled, or watermarked, across an end user screen behind the text of an e-mail message or public posting. A message server inserts the background reference after receiving a message originally sent from an end user originator and before sending the message to be delivered to an end user recipient. When necessary, the message server will convert at least a portion of the message into a proper format, such as HTML, before inserting the background reference to an advertisement, which is preferably selected in accordance with end user recipient demographic information and/or ad exposure statistics. The advertisement itself, often a graphical file, is preferably not transmitted with the message in some preferred embodiments of the invention, but is typically stored at the message server or other location remote from the end user recipient. In some embodiments, the message server will also maintain and refer to records on each end user recipient to allow for selective enablement of background reference insertion and overwriting based upon end user preferences. According to various “non-web” example embodiments, the message server receives an SMTP or NNTP message and transmits an SMTP, POP3 or NNTP message with an HTML portion for a respective HTML-compatible client. In other “web-based” embodiments, the message server transmits the entire message in HTML to be used as a stand-alone web page or as a portion of a larger page employing frames or tables.
[0014] Since the advertisement is placed in the background when viewed by a user, it is normally non-clickable, i.e., not a hyperlink to another HTML page. While this novel system of advertising is unusual since a typical user may initially desire, as with conventional banner advertisement, to click on the background image to go to another web page owned by the advertiser for more information or for ordering a product, the user will often be exposed to the tiled advertisement longer, and many times subliminally, while reading the content of the message, and the user may also be initially surprised to see an advertisement in the background of an e-mail message which may be from a known originator, thus increasing the awareness and exposure. Background images may also be very small in comparison to banner advertisements, thus downloading relatively quickly. While the scope of the present invention is also intended to include inserting a reference to any type of background image or graphic, including non-advertisements, the method of inserting a reference to an advertisement is considered particularly useful and beneficial in view of the above unexpected advantages, among others. In addition, Internet service providers, web site owners, e-mail service providers, newsgroup services and other end user communication providers are able to extract revenue for non-obtrusive advertising on 100% of the active screen area while still providing a work area for users to perform desired functions. In addition, this display does not necessarily affect current advertisement banners being displayed. Other features and advantages of various preferred embodiments of the present invention will become apparent to one with skill in the art upon examination of the following drawings and detailed description.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
[0015] The accompanying drawings incorporated in and forming a part of the specification illustrate several aspects of the present invention, and together with the description, serve to explain the principles of the invention.
[0016] [0016]FIG. 1 is a block diagram illustrating physical components of one implementation of the present invention.
[0017] [0017]FIG. 2 is a block diagram illustrating one type of end user workstation in accordance with one preferred embodiment of the present invention.
[0018] [0018]FIG. 3 is a block diagram illustrating one type of network server in accordance with one preferred embodiment of the present invention.
[0019] [0019]FIG. 4 is a flowchart showing general operation steps of the background reference system of the present invention in accordance with one preferred embodiment.
[0020] [0020]FIG. 5 is a flowchart showing the operation of one implementation of a background reference insertion process of FIG. 4.
[0021] [0021]FIG. 6 is an illustration of selected basic components of an example end user e-mail communication message as sent by an end user originator, in accordance with one preferred embodiment of the present invention.
[0022] [0022]FIG. 7 is an illustration of the end user e-mail communication message of FIG. 6 converted completely into HTML for use in a web-based e-mail implementation of one preferred embodiment of the present invention.
[0023] [0023]FIG. 8 is an illustration of the message of FIG. 7 with an inserted advertising background reference.
[0024] [0024]FIG. 9 is an illustration of a screen display of the message of FIG. 8.
[0025] [0025]FIG. 10 is a flowchart showing the general operation of another preferred embodiment of the present invention in a non-web-based, SMTP/POP3 implementation of a background reference system accommodating an e-mail message with an attachment.
[0026] [0026]FIG. 11 is an illustration of selected basic components of an example end user e-mail communication message that is not in MIME format and that has an attachment, in accordance with the preferred embodiment of FIG. 10.
[0027] [0027]FIG. 12 is an illustration of an example message similar to that of FIG. 11 converted into MIME format.
[0028] [0028]FIG. 13 is an illustration of an example message similar to that of FIG. 12 converted into a multipart/alterative part MIME format with an HTML part including a background reference.
[0029] [0029]FIG. 14 is an object model diagram showing portions of one implementation of an advertising system in accordance with one preferred embodiment of the present invention.
[0030] [0030]FIG. 15 is a flowchart showing a configuration process of the advertising system implementation portion represented by FIG. 14.
[0031] [0031]FIG. 16 is a flowchart showing selected e-mail processing steps of the advertising system implementation portion represented by FIG. 14.
[0032] Reference will now be made in detail to the description of the invention as illustrated in the drawings. While the invention will be described in connection with these drawings, there is no intent to limit it to the embodiments disclosed therein. On the contrary, the intent is to cover all alternatives, modifications and equivalents included within the spirit and scope of the invention as defined herein and by the appended claims.
DETAILED DESCRIPTION OF THE INVENTION
[0033] Turning now to the drawings, wherein like reference numerals designate corresponding parts throughout the drawings, FIG. 1 is a block diagram illustrating physical components 10 of one implementation of the present invention, which has flexibility, expandability, and platform independence. While system configuration can take many forms in accordance with scope of the present invention, the diagram of FIG. 1 illustrates a plurality of end user workstations 11 , 12 , 13 and 14 directly connected to networks 18 and 19 , acceptable examples of which include, among others, local area networks (LANs) and Intranets. Additional workstations 20 , 22 are remotely located and in communication with the network 18 through a remote access network 24 . Network servers 26 , 28 , and 30 , one or more of which are capable of functioning as a message server to perform the background reference insertion methods in accordance with the present invention, as discussed below, are shown connected to each other through an Internet 32 , with conventional routers and switches omitted for clarity, but understood by those reasonably skilled in the art of the present invention. Such network servers are configured to support one or more conventional communication protocols, including, but not limited to, SMTP, POP3, IMAP, NNTP, HTTP, etc. Of course, the elements of FIG. 1 are understood to be representative of multitudes of similarly connected components, and various types of conventional workstations are understood to be connected to the Internet 32 through conventional schemes.
[0034] In one application of the physical components 10 , one end user organization owns and maintains the components directly connected to network 18 , and another end user organization owns and maintains the components directly connected to network 19 . In that application, the network server 28 can be configured to insert background references into end user communications originated and received by any of the workstations 11 , 12 , 13 , 14 , 20 , 22 . For example, if an end user at workstation 20 sends an e-mail message to an end user at workstation 12 , such a message could be routed through network server 26 , network server 28 for background reference insertion, and then network server 30 . Though not necessary, such routing could be prompted by the end user at workstation 12 maintaining an e-mail mailbox on network server 28 . In another of the many applications of the physical components 10 included in the scope of the present invention, network server 26 is maintained by an Online Service Provider (OSP) to provide OSP customers using workstations 20 , 22 access to the Internet 32 , including e-mail mailboxes and access to the web and public messaging. In one example use of such an application, e-mail messages or public postings originated and/or received by an OSP customer would include background references inserted by network server 26 , including those from and/or to other customers of the OSP and others outside the OSP, as configured by the OSP. As with the former application, OSP customers may also maintain mailboxes on network server 28 . Clearly, these applications are merely examples, and other applications of the physical components 10 are also contemplated such that any network server is capable of functioning as a message server to perform the background reference insertion method of the present invention, as discussed below, without regard to whether mailboxes or user accounts are maintained by the message server.
[0035] Refer now to FIG. 2, which is a block diagram illustrating one type of end user workstation 11 , in accordance with one preferred embodiment of the present invention. A local interface 38 , such as a conventional computer bus, is shown connected to a variety of components, including a storage unit 40 , a processor 42 , an input device interface 44 providing an interface to the local interface 38 for a conventional keyboard 46 and mouse 48 , a display 50 for displaying information for being viewed by a user, a modem/network interface 55 for providing connectivity to other computers and networks, and memory 95 . One example, among others, of an acceptable storage device 40 is a conventional hard drive, which is used for non-volatile storage of programs and other data which are loaded into memory 95 for operation of the workstation 11 and used by processor 42 to control operation of the workstation 11 . Such programs (also referred to as applications, systems, software, etc.) typically include, among others, an operating system 96 , a browser client 52 , an e-mail client 53 , and a public posting client 54 . Examples of acceptable operating systems 96 include, among others, Microsoft® Windows® and Unix. Examples of acceptable browser clients 52 include, among others, Microsoft® Internet Explorer and Netscape Navigator. One example, among others, of an acceptable e-mail client is Eudora Pro Email v4.0. One example, among others, of an acceptable public posting client 54 is Microsoft® Outlook Express, which also functions as an acceptable e-mail client. Some web browser clients also function as non-web-based newsgroup and e-mail clients, thus also serving as enhanced readers of NNTP and POP3 information. Of course, the scope of the present invention is intended to include, but not be limited to, any client capable of displaying end user information with a definable background from any type of electronic feed, including but not limited to, web pages, e-mail messages, public postings, etc.
[0036] Referring back to FIG. 1, one example implementation and application of the present invention includes the network server 28 functioning as a message server for inserting advertisement background references into end user messages. Refer now to FIG. 3, which shows a block diagram representation of selected elements of one type of network server 28 , which is shown including hardware elements similar to those of the example workstation 11 shown in FIG. 2. For example, a local interface 138 , such as a conventional computer bus, is shown connected to a variety of components, including a storage unit 140 , a processor 142 , an input device interface 144 providing an interface to the local interface 138 for a conventional keyboard 146 and mouse 148 , a display 150 , a modem/network interface 160 for providing connectivity to other computers and networks, and memory 195 . One example, among others, of an acceptable storage device 140 is a conventional hard drive, which is used for non-volatile storage of software programs and other data which are loaded into memory 195 for operation of the network server 28 and used by processor 142 to control operation of the network server 28 . However, the network server 28 executes software programs (also referred to as applications, systems, software, etc.) which are different from those of the workstations. For example, in accordance with one implementation, software executed by the network server 28 executes a web server 152 , e-mail server 153 , public posting server 154 , such as a newsgroup server, and background reference system 155 . In other implementations, network server 28 executes background reference system 155 in combination with one or more of the web server 152 , public posting server 154 , e-mail server 153 , or other end user message server software. In addition, while one implementation of the present invention includes separate background reference system 155 which communicates with one or more end user message server software programs, other implementations include integrated end user message software solutions which directly incorporate the functionality of the background reference system 155 .
[0037] In addition, the background reference system 155 of the present invention can be implemented in hardware, software, firmware, or a combination thereof. In one preferred embodiment, the background reference system 155 is implemented in software or firmware that is stored in a memory and that is executed by a suitable instruction execution system. The background reference system 155 , which comprises an ordered listing of executable instructions for implementing logical functions, can be embodied in any computer-readable medium for use by or in connection with an instruction execution system, apparatus, or device, such as a computer-based system, processor-containing system, or other system that can fetch the instructions from the instruction execution system, apparatus, or device and execute the instructions. Examples, among many others, of acceptable software implementation environments include Java, Javascript, C++, etc. In the context of this document, a “computer-readable medium” can be any means that can contain, store, communicate, propagate, or transport the program for use by or in connection with the instruction execution system, apparatus, or device. The computer readable medium can be, for example but not limited to, an electronic, magnetic, optical, electromagnetic, infrared, or semiconductor system, apparatus, device, or propagation medium. More specific examples (a nonexhaustive list) of the computer-readable medium would include the following: an electrical connection (electronic) having one or more wires, a portable computer diskette (magnetic), a random access memory (RAM) (magnetic), a read-only memory (ROM) (magnetic), an erasable programmable read-only memory (EPROM or Flash memory) (magnetic), an optical fiber (optical), and a portable compact disc read-only memory (CDROM) (optical). Note that the computer-readable medium could even be paper or another suitable medium upon which the program is printed, as the program can be electronically captured, via for instance optical scanning of the paper or other medium, then compiled, interpreted or otherwise processed in a suitable manner if necessary, and then stored in a computer memory.
[0038] Refer also to FIG. 4, which is a flowchart showing general operation steps 300 of the background reference system 155 of the present invention, in accordance with one preferred embodiment. The background reference system 155 receives an end user communication message in step 304 , such as, for example, through an SMTP or NNTP gateway from the Internet 32 (FIG. 1), through a POP3 or IMAP mailbox, or through any other communication connection method for intercepting or otherwise accessing an end user communication message sent toward at least one end user recipient from an end user originator. The background reference system 155 determines if the received message is in a format, such as HTML as one example, that can accept a reference to a background, such as an advertising image as one example. If the message is not in such a format, such as plain text as one example, the message is converted into an appropriate format to accept a background reference, as indicated in step 308 . If the message is already in such a format, or after the message is converted into such a format in step 308 , an appropriate background reference is added to the message, such as through a background reference insertion process 312 , an example of one implementation of which is shown in FIG. 5 and discussed below. Subsequently, as indicated in step 314 , the end user message is made available for delivery to one or more end user recipients. In some embodiments and implementations of the present invention, this step includes sending and actually delivering the message to one more end users in user dependent formats.
[0039] Refer now to FIG. 5, which shows the operation of one implementation of the background reference insertion process 312 of FIG. 4. The implementation of FIG. 5 is related to an advertisement system, but it should be understood that the present invention includes inserting references to any type of background into end user messages. In addition, included in the scope of the present invention are practically all technologies through which a background, tiled or not tiled on an end user recipient's screen, is designated for an end user communication message, including client-based solutions and future technologies for accomplishing the described functions. Nonetheless, it should be clear that while the scope of the present invention is also intended to include inserting a reference to any type of background image, graphic, etc., including non-advertisements, the method of inserting a reference to an advertisement is considered particularly useful and beneficial, as discussed above.
[0040] According to the implementation of FIG. 5, it is first determined at step 404 whether the message already includes a background reference. While some embodiments of the present invention include determining if any type of background reference is specified, including a mere designation of a color, other embodiments include checking only for a designation of a separate image file as a background. In addition, some embodiments will include making this determination only for messages previously determined in step 306 to already be in a format that can accept a background reference since such messages are more likely to already include a background reference. If the message already includes a background reference, step 406 determines if an approval configuration specifies whether the background reference can be overwritten with a new background reference. If the approval configuration indicates that background references are not to be overwritten for a particular message, step 412 indicates that the background reference insertion process 312 terminates without overwriting the existing background reference. An approval configuration file is maintained in one embodiment of the present invention in order to enable end user recipients to configure the background reference system 155 (FIG. 3) on whether or not to overwrite existing background references in messages received by them. In other embodiments, steps 404 and/or 406 are omitted, whereby there is automatic overwriting of all or no existing background references. Furthermore, the ordering of steps in the various flowcharts of the present invention are not intended to limit the scope of the present invention with respect to order of operation since other embodiments include varying the orders of the steps. As one example, in some embodiments, steps 404 , 406 and 412 are instead executed after a message is received and before format determination is made in step 306 . In still other embodiments, a general approval determination is included before format determination in order to determine if a particular end user recipient has approved any background reference insertions, regardless of whether any background references already exist.
[0041] In accordance with the implementation shown in FIG. 5, when the background reference system 155 determines that an existing background reference may be overwritten in step 406 , or if it is determined that there is no background reference specified in step 404 , then further determinations are made as to which advertisement should be referenced by a new background reference to be inserted (or overwritten if already present) into the message. Based on a determination in step 408 , advertisements may be selected by the background reference system 155 based on available demographic information for a particular end user recipient (step 414 ) and/or on advertiser and advertisement exposures (step 416 ). In a web-based “free” e-mail implementation, acquisition of demographic information is required before the e-mail account is provided to a user. If demographic information is not available or is otherwise inconclusive for targeted advertisements, commitments to advertisers may drive the selection from a pool of available advertisers. Of course, as advertisements are selected based on demographic categories or exposure requirements, records are maintained for future selection and reporting purposes. There are many conventional demographic and advertisement pool processing systems currently available and understood by those reasonably skilled in the art of the present invention. Although only two types of advertisement selection criteria have been discussed, it should be understood that other criteria can be used without departing from the spirit of the present invention. Of course, advertisements should be constructed in color and design to not interfere with end user recipients being able to read the foreground message text.
[0042] Once an appropriate advertisement has been selected in steps 414 or 416 , a background reference to that advertisement is inserted into the message at step 418 . In one implementation of the present invention in HTML, a background tag, such as <body background=“AdvertisementFile”>, is inserted into an HTML portion of a message, where “AdvertisementFile” is the name of a stored advertisement file. The advertisement file itself, often a graphical file, is preferably not transmitted with the message in some preferred embodiments of the invention, but is typically stored at the message server or other location remote from the end user recipient. In web-based embodiments, the background file may be co-located, and in a similar storage directory or folder, with the web page message or located remotely from the web page message. If the background file is co-located with the web page message in the same storage directory or folder, the background reference need only include the name of the background file. Otherwise, preamble directory names or full URL addresses beginning with “http://www”, etc., are necessary since the background file can be located anywhere on the Web in some embodiments.
[0043] In some web-based embodiments where messages are stored on a network server after viewing by an end user recipient, the background reference insertion steps of the present invention are repeated each time the end user views the message to show the end user a different background each time the message is viewed. In addition, in other embodiments, regardless of whether those embodiments are web-based, the actual background file referenced by the background reference is changed so that the end user recipient views a different background when the message is viewed subsequently. In still other embodiments, the URL is not an actual address of a known file, but a call to a separate server program, or script, to supply an unknown particular file chosen by the server program. Since the particular file supplied will automatically vary in some embodiments, end user recipients see different backgrounds each time the message is viewed. While apparently never having been associated with the insertion of background references into end user communication messages, some methods of calling a server program, or script, for receiving an unknown particular file are conventional and would be understood by those reasonably skilled in the art of the present invention, and are included within the scope of the present invention.
[0044] Some other embodiments include transmitting the advertisement file as an attachment along with the message for storage on an end user recipient workstation. Of course, configuration or knowledge of the end user recipient downloading location would be necessary (e.g., c:\downloadfolder\) in constructing the proper address in the background reference of the downloaded advertisement, which would only need to be downloaded once in embodiments tracking which advertisements are downloaded to which end user recipients and selectively sending only those advertisements that have not previously been sent to particular end user recipients.
[0045] [0045]FIG. 6 shows an illustration of selected basic components of an example end user e-mail communication message as sent by an end user originator, in accordance with one preferred embodiment of the present invention. Additional conventional header information is not shown for purposes of clarity, as is also often selectively the case with conventional e-mail clients. Referring also back to FIG. 4, if a message represented by the example message of FIG. 6 is received in step 304 of FIG. 4, it would be subsequently determined in step 306 that the message is not in format that can accept a background reference since the message is in plain text. Consequently, in step 308 , the message would be converted into an appropriate format, such as HTML, an example of which is shown in FIG. 7. If, instead, a message represented by FIG. 7 was initially received at step 304 , i.e., one which includes an HTML portion, as an example, it would already be in an appropriate format, and step 308 would not be executed. Subsequently, as discussed above with respect to background reference insertion process 312 , a background reference is inserted into the message, an example of which is shown in FIG. 8. The example background reference shown in FIG. 8 is <body background=“http://www.exampledomain.com/tkhr_ad.jpg”>. As discussed above, in some web-based embodiments storing advertisements in the same directory or folder as web page messages, the preamble can be omitted; thus, in the example shown in FIG. 8, the preamble “http://www.exampledomain.com/” could then be omitted.
[0046] [0046]FIG. 9 shows an illustration of a screen display of the example message of FIG. 8, where a tiled background image of a diagonal “www.tkhr.com” is shown as an example. Again, this image is not “clickable” since it is in the background of the screen, but e-mail messages and other end user communications can be branded, or watermarked, with virtually any background image as shown. In one implementation of a web-based e-mail system, the entire browser viewing area is used for displaying the message and background image, thus control buttons such as reply, reply all, forward, delete, close, download attachment, etc. are on another screen and are accessible by a back button on a browser, as is conventionally available in other web-based e-mail systems. In another implementation, the information shown in FIG. 9 is placed in a frame or table to share the browser viewing area with one or more other frames and/or tables containing controls. In yet another implementation, control buttons and additional information is inserted into the message itself. Of course, traditional banner advertisements may still be displayed in addition to the background.
[0047] Refer now to the FIG. 10, which is a flowchart showing general operation steps 500 of another preferred embodiment of the present invention in a non-webbased, SMTP/POP3 implementation of a background reference system accommodating an e-mail message with an attachment. This example is useful for end user recipients with MIME-compatible and HTML-compliant e-mail clients. In the example shown, after receiving a message in step 504 , it is determined if the message is in a conventional MIME format in step 506 . In this preferred embodiment, this determination can be performed by searching the message for the text “MIME-Version”, for example, in a header field. Although this is the search criteria in this preferred embodiment, it should be understood that the scope of the present invention includes any search criteria that may be used in identifying whether a message is MIME formatted. If the message is not in a MIME format, it is checked for attachments included within the text of the message and converted into a MIME format in step 908 . One such type of attachment is the conventional UUENCODED attachment, which is delineated by keywords “begin” and “end”; hence, in this preferred embodiment, the message is checked for characteristic placement of these keywords. Once converted, the message will include a “MIME-Version” header field, and any attachment will be converted into a MIME attachment portion. One example attachment conversion process includes converting from UUENCODE to base 64 , which is well defined and documented in Request for Comments (RFC) 2045 , which is considered understood by those skilled in the art of the present invention and which is herein incorporated by reference. The converted attachments will be added as parts to the message, including the addition of separators as discussed in more detail in RFC 2045 .
[0048] Next, a MIME multipart/alternative part with HTML is added in step 510 . The multipart/alterative designation offers an alternative version of the text of the message such that clients that support HTML can display it, and clients that do not can show the other alternative, which is usually plain text. The HTML part is essentially an HTML version of the e-mail message, the conversion to which would be understood by those reasonably skilled in the art of the present invention as similar to that discussed above with respect to step 308 (FIG. 4). If the message received in step 506 is already in a MIME format, it is determined in step 511 whether the message already contains an HTML part, such as through searching for an appropriately located string “text/html”. If not, step 510 is executed as discussed previously. If so, as well as after step 510 is executed in the other two circumstances discussed previously, a background reference insertion process is executed in step 512 , which is similar to the background reference insertion process 312 shown in FIG. 5. As with the embodiment discussed in FIGS. 4 and 5, the ordering of steps is changed in other embodiments, and previous determinations may affect subsequent determinations. For example, if it is known through steps 508 or 511 that the message does not contain an HTML part, steps 404 , 406 , and 412 need not be executed since it would already be known that no background reference is specified.
[0049] [0049]FIG. 11 is an illustration of selected basic components of an example end user e-mail communication message that is not in MIME format and that has an attachment, in accordance with the preferred embodiment of FIG. 10. The attachment, “clouds.bmp”, is shown in a UUENCODED format between, and including, the words “begin” and “end.” FIG. 12 is an illustration of an example message similar to that of FIG. 11 converted into MIME format with the attachment in base 64 encoding. FIG. 13 is an illustration of an example message similar to that of FIG. 12 converted into a multipart/alterative part MIME format with an HTML part including a background reference. The HTML part begins with <HTML> and ends with </HTML>, and the example background reference is shown as <body background=“http://www.exampledomain.com/tkhr_ad.jpg>. In an HTML-compatible, MIME-compliant e-mail client, the “clouds.bmp” attachment would be downloaded to the end user recipient's workstation, and the e-mail message would be displayed with a tiled background of the image file located at the referenced address. The “clouds.bmp” file is not intended to be the background file in this preferred embodiment, but as discussed above, other embodiments include sending the background file along as an attachment to the message. Thus, if the “clouds.bmp” file were the intended background file, and if it were known that the download directory on the end user recipient workstation was “c:\download”, then the background reference would be similar to <body background=“c:\download\clouds.jpg”>.
[0050] Refer now to FIG. 14, which is an object model diagram 600 showing portions of one implementation of an advertising system in accordance with one preferred embodiment of the present invention. The method employed by the diagram 600 , also known as a Rose model, is a unified modeling language, (UML), a standardized way of representing objects and their relationships to each other. In the diagram 600 , a hollow arrow “inherits” (a first object inherits from a second object if the first object takes on the properties and behavior of the second object, i.e., the first object contains the properties and methods of the second object), a dotted line with an arrow is a dependency (using an object internally or during a function call as a parameter) and a straight solid line is an “association” (using an object internally without exposing it). Boxes shown in the diagram are object classes, which include member variables and methods. The letter “Z” merely signifies that the element is an object, i.e., standing for “the.”
[0051] Thus, a ZVendorSpecificEmailInterface 610 inherits from a ZEMailInterfaceBase 612 ; a ZVendorSpecificDemographicInterface 614 inherits from a ZDemographicInterfaceBase 616 ; ZVendorSpecificApprovalInterface 618 inherits from a ZApprovalInterfaceBase 620 ; and a ZHTMLEMail 622 inherits from both a ZEMailBase 624 and a string 626 . A ZWatermarker 628 has a dependency on the ZEMailInterfaceBase 612 , the ZDemographicInterfaceBase 616 , and the ZApprovalInterfaceBase 620 , as well as an association with the ZHTMLEMail 622 and the ZEMailBase 624 . The ZEMailInterfaceBase 612 also has dependencies on the ZHTMLEMail 622 and the ZEMailBase 624 . The ZEMailBase 624 has dependencies on the string 626 and a ZAttachment 632 , as well as associations with a list<String> 630 and a list<ZAttachment> 634 , both of which are aggregates of a list<Type> 636 and themselves have dependencies on the string 626 and ZAttachment 632 , respectively. The ZApprovalInterfaceBase 620 has a dependency on the ZEMailBase 624 . The list<Type> 636 is a template class corresponding to a standard template library for dynamic compilation. A template class is a class which, at compile time, takes parameters passed to it and replaces those parameters internally. The ZEMailBase 624 contains Zattachment 632 and string 626 to store its contents.
[0052] Member variables and methods for the objects of FIG. 14 include the following, with colons “:” meaning “type” for members and “return type” for methods:
ZAttachment 632
[0053] MEMBERS
[0054] m_ulLength: Long=0
[0055] m_pBinaryData: void*=NULL
[0056] m_Name: String=“”
[0057] METHODS
[0058] ZAttachment ( )
[0059] GetData ( ): void*
[0060] PutData (pData: void*=default, lDataLength long=default):
[0061] enumSuccessError
ZEMailBase 624
[0062] MEMBERS
[0063] m_RecipientList: list<String>
[0064] m_CarbonCopyList: list<String>
[0065] m_Date: Date
[0066] m_sSender: String
[0067] m_sSubject: String
[0068] m_sBody: String
[0069] m_AttachmentList: list<ZAttachment>
[0070] m_IReferenceID: Long=0
[0071] m_sMailBoxName: String
[0072] METHODS
[0073] GetRecipientCount ( ): Long
[0074] GetRecipient (lIndex: Long): String
[0075] GetCarbonCopyCount ( ): Long
[0076] GetCarbonCopy (lIndex: Long): String
[0077] GetDate ( ): Date
[0078] GetSender ( ): String
[0079] GetSubject ( ): String
[0080] GetBody ( ): String
[0081] GetAttachmentCount ( ): Long
[0082] GetAttachment ( ): ZAttachment
[0083] GetReferenceID ( ): Long
[0084] GetMailBoxName ( ): String
ZHTMLEMail 622
[0085] METHODS
[0086] ZHTMLEMail (EMailBaseToCopy: ZEMailBase&)
[0087] Construct (EMailBaseToCopy: ZEMailBase&): enumSuccessError
[0088] AddBackground (sBackgroundReference: String): enumSuccessError
ZWatermarker 628
[0089] MEMBERS
[0090] m_pEMailInterfaceBase: ZEMailInterfaceBase*=NULL
[0091] m_pDemographicIInterface: ZDemographicInterface*=NULL
[0092] m_pApprovalInterface: ZApprovalInterfaceBase*=NULL
[0093] METHODS
[0094] PutEmailInterface (pEMailIInterface: ZEMailIInterfaceBase*): enumSuccessError
[0095] PutDemographicInterface (pDemographicInterface: ZDemographicInterfaceBase*) : enumSuccessError
[0096] PutApprovalInterface (pDemographicInterface: ZApprovalInterfaceBase*=default): enumSuccessError
[0097] ProcessEMail (IReferenceID: Long): enumSuccessError
[0098] ConvertEMail ( ): enumSuccessError
ZEMailInterfaceBase 612
[0099] METHODS
[0100] Register (pWatermarker: ZWatermarker*): enumSuccessError
[0101] GetEMail (IReferenceID: DataType): ZEMailBase
[0102] PutEMail (HTMLEMail: ZHTMLEMail&): enumSuccessError
ZDemogarhicInterfaceBase 616
[0103] METHOD
[0104] GetBackgroundReference (MailBoxName: String): String
ZApprovalInterfaceBase 620
[0105] METHOD
[0106] IsApproved (rEMailBase: const ZEMailBase&=default): BOOL
[0107] Each of the vendor specific objects, including ZVendorSpecificEmailInterface 610 , ZVendorSpecificDemographicInterface 614 , and ZVendorSpecificApprovalInterface 618 , are constructed to interface with specific vendor systems. Thus, such objects may be interchanged and used as necessary when working with different systems. Furthermore, the ZVendorSpecificEmailInterface 610 is replaced with a ZVendorSpecificNewsgroupInterface for NNTP interfacing, as well as any other type of end user messaging system needed.
[0108] Refer also to FIG. 15, which is a flowchart showing a configuration process 700 of the advertising system implementation portion represented by FIG. 14. When configuration process 700 software is compiled, a determination is made regarding the operating system environment, such as Windows or Unix. After that determination is made, the compiled software runs according to the operating system distinctions shown, but the determination is made only once. Thus, after it is determined that Unix or Windows is the operating environment for a particular implementation, all of the illustrated operating system determinations 704 , 718 , 726 , and 734 are already determined. After the process 700 starts in step 702 , a manual process, if Unix is the operating system, three daemons are manually started in steps 706 , 708 , and 710 , including a vendor specific email interface daemon, a vendor specific demographic interface daemon, and a vendor specific approval interface daemon, respectively.
[0109] Subsequently, a watermarker container program is manually started in step 712 . The watermarker container program then instantiates, creates an instance of, ZWatermarker 628 in step 714 . Subsequently, in step 716 , the watermarker container program creates an instance of the ZEMailInterfaceBase 612 , after which either a vendor specific EMailInterface DLL is loaded (step 720 ) or communication is established to a vendor specific EMailInterface daemon (step 722 ), depending on the operating system in which the process 700 software is compiled, as discussed above. Then, in step 724 , the watermarker container program creates an instance of the ZApprovalInterfaceBase 620 , after which either a vendor specific ApprovalInterface DLL is loaded (step 728 ) or communication is established to a vendor specific ApprovalInterface daemon (step 730 ), depending on the operating system in which the process 700 software is compiled, as discussed above. In step 732 , the watermarker container program creates an instance of the ZDemographicInterfaceBase 616 , after which either a vendor specific DemographicInterface DLL is loaded (step 736 ) or communication is established to a vendor specific DemographicInterface daemon (step 738 ), depending on the operating system in which the process 700 software is compiled, as discussed above.
[0110] The watermarker container program then passes the ZApprovalInterfaceBase 620 to the ZWatermarker 628 in step 740 , which calls the PutApprovalInterface method in the ZWatermarker 628 . The watermarker container program passes the ZEMailInterfaceBase 612 to the ZWatermarker 628 in step 742 , which calls the PutEMailInterface method in the ZWatermarker 628 , which then prompts the ZWatermarker 628 , in step 744 , to call ZEMailInterfaceBase::Register to enable the ZEMailInterfaceBase 612 to trigger work. In step 746 , the watermarker container program passes the ZDemographicInterfaceBase 616 to the ZWatermarker 628 , which calls the PutDemographicInterface method in the ZWatermarker 628 . Although the watermarker container program is then finished initializing, the process 700 waits in step 748 for the ZEMailInterfaceBase 612 to trigger work in response to receiving an e-mail message as discussed below.
[0111] Refer also to FIG. 16, which is a flowchart showing selected e-mail processing steps 800 of the advertising system implementation portion represented by FIG. 14. After an e-mail message is received in step 802 , through the ZVendorSpecificEmailInterface 610 , the ZEMailInterfaceBase 612 calls, in step 804 , the ZWatermarker::ProcessEmail method in the ZWatermarker 628 with an EMail reference ID (identification number). Step 802 may include being notified by an external brand-specific e-mail server program through the ZVendorSpecificEmailInterface 610 that a new e-mail message is in a particular mailbox. In other embodiments, the ZVendorSpecificEmailInterface 610 polls the external e-mail server program to determine when a new e-mail message is available. When the ZWatermarker 628 is available in step 806 , it retrieves the e-mail message from the ZEMailInterfaceBase 612 as a ZEMailBase 624 object using the previously supplied reference ID. The ZEMailBase 624 is a data container that parses the received e-mail message so that the ZWatermarker 628 can operate on e-mail messages regardless of format. Subsequently, in step 808 , the ZWatermarker 628 passes the ZEMailBase 624 object to the ZApprovalInterfaceBase:IsApproved method of the ZApprovalInterfaceBase 620 , which examines the ZEMailBase 624 object to determine if further processing is necessary, as determined by a separate approval system with which the ZVendorSpecificApprovalInterface 618 interfaces. As discussed above, this separate approval system functions in accordance with an approval configuration for each end user recipient which, in some embodiments, determines if an existing background reference exists and if it is to be overwritten. In other embodiments, certain users may be configu red to have all background references overwritten, and in other embodiments, the insertion of background references is approved based on other demographic or message content factors. As determined in decision step 810 , if the ZApprovalInterfaceBase:IsApproved method returns false, the process 800 essentially terminates and waits for another incoming e-mail message in step 812 . Otherwise, processing continues in step 814 .
[0112] In step 814 , the ZWatermarker 628 retrieves the MailBoxName from the ZEMailBase 624 object. Subsequently, in step 816 , the ZWatermarker 628 begins the process of obtaining an appropriate background reference by calling the ZDemographicInterfaceBase::GetBackgroundReference method of the ZDemographicInterfaceBase 616 and supplying the MailBoxName. Then, in step 818 , separate demographic software, to which an interface is provided through ZVendorSpecificDemographicInterface 614 , determines the appropriate background reference for the supplied MailBoxName. In step 820 , the ZWatermarker 628 converts the ZEMailBase 624 object to a ZHTMLEMail 622 object with a provided copy constructor. Since the ZHTMLEMail 622 inherits from the ZEMailBase 624 , the ZHTMLEMail 622 has access to all of the data and structure of the ZHTMLEMail 622 object for making an HTML copy. As discussed above, conversion to HTML includes a complete conversion for webbased applications, and conversion of a portion of the e-mail message for non-web-based applications. In addition, attachments are also handled at this point as discussed above, as well as the creation of control buttons for general control and for downloading any attachments through server scripting in web-based applications. Then, in step 822 , the ZWatermarker 628 calls the ZHTMLEMail::AddBackground method of the ZHTMLEMail 622 with the appropriate background reference, which is inserted into the HTML of the ZHTMLEMail 622 object. In step 824 , the ZWatermarker 628 returns the newly formatted ZHTMLEMail to the ZEMailInterfaceBase by calling the PutEmail method, which includes placing the ZHTMLEMail 622 object in an appropriate place for making the message available for delivery to an end user recipient. Subsequently, the process 800 waits for the next e-mail message in step 812 .
[0113] In other embodiments of the present invention, the RecipientList and CarbonCopyList variables of the ZEMailBase 624 object for each e-mail message are used to generate associational demographic information. In other words, marketing conclusions can be drawn about other primary recipients and carbon copy recipients based on demographic information of one intended end user recipient. Thus, this information is useful and easily tracked and reported in accordance with the present invention.
[0114] In concluding the detailed description, it should be noted that it will be obvious to those skilled in the art that many variations and modifications can be made to the preferred embodiment without substantially departing from the principles of the present invention. All such variations and modifications are intended to be included herein within the scope of the present invention, as set forth in the following claims. | An advertisement system and method are provided for inserting into an end user communication message a background reference to an advertisement. In some embodiments, the background reference causes an advertisement image to be tiled, or watermarked, across an end user screen behind the text of an e-mail message or public posting. A message server inserts the background reference after receiving a message originally sent from an end user originator and before sending the message to be delivered to an end user recipient. When necessary, the message server will convert at least a portion of the message into a proper format, such as HTML, before inserting the background reference to an advertisement, which is preferably selected in accordance with end user recipient demographic information and/or ad exposure statistics. The advertisement itself, often a graphical file, is preferably not transmitted with the message, but is typically stored at the message server or other location remote from the end user recipient. Preferably, the message server maintains and refer to records on each end user recipient to allow for selective enablement of background reference insertion and overwriting based upon end user preferences. According to various “non-web” example embodiments, the message server transmits an SMTP, POP3 or NNTP message with an HTML portion for a respective HTML-compatible client. In other “web-based” example embodiments, the message server transmits the entire message in HTML to be used as a stand-alone web page or as a portion of a larger page employing frames or tables. | 6 |
BACKGROUND OF THE INVENTION
A tool holder is clamped in the spindle of a machine tool. The structure for clamping the tool holder therein is as shown in FIG. 6.
In this figure, 1 points out a spindle body rotatably supported in the spindle head. A tapered hole 1a into which the tapered section 2a of the tool holder 2 is inserted is formed at the tip end. Thereof, and an operating hole 1b on which a staged portion "m" is formed at the upper part thereof is provided. 3 points out a sleeve which is inserted in the corresponding operating hole 1b and is engaged with at the position of the staged portion "m", and the diameter of the lower portion of the inner hole 3a thereof is set to a larger value than that of the upper portion thereof. And a draw bar 4 is pulled upwards by elongation force of a coned disk spring 5 and is so arranged that it can be displaced downwards. The lower end 4a thereof is provided with a cylindrical hole 4c, and a plurality of through holes 4b are provided in the direction of radius with a proper interval in the inward direction at the inlet side thereof. Balls 6 are inserted in the through holes 4b and are so composed that they can engage with the pull stud 2b of the tool holder 2.
In such a structure as shown in the above, when clamping the tool holder 2, the draw bar 4 is displaced toward the downward direction as shown with an imaginary line "n" in the figure against the elongation force of the coned disk spring 5. Under this condition, the tool holder 2 is inserted from downwards toward inwards of the tapered hole 1a of the spindle 1, thereby causing the pull stud 2b of the tool holder 2 to arrive at the solid line position in the figure, excluding the ball 6 outwards of the through holes 4b. Thereafter, the draw bar 4 is made free and is displaced upwards by elongation force of the coned disk spring 5, thereby causing the ball 6 to move inwardly in the through holes 4b with the outer surface thereof guided in the inner hole 3a of the sleeve 3 and to reach the solid line position in the figure where the pull stud 2b is engaged and fixed. Thereafter, this condition is continuously maintained.
To the contrary, when unclamping the tool holder 2, the draw bar 4 is displaced toward the downward direction as shown with an imaginary line "n" in the figure against the elongation force of the coned disk spring 5 as mentioned above, thereby causing the tool holder 2 to be released.
In order to acquire a strong force by the conventional structure, it is necessary to increase the elongation force of the coned disk spring 5 according to the increment of the clamping force.
However, increasing the elongation force of the coned disk spring 5 results in increase of the operating force of the draw bar 4 when clamping and unclamping the tool holder 2, and increase of the corresponding operating force further derives a new problem, that is, increase of the thrust of bearings by which the spindle 1 is supported.
Under such a circumstance, a spindle structure by which the tool holder 2 is strongly clamped to the spindle 1 without excessively increasing the elongation force of the coned disk spring 5 is much desired.
Also, if the draw bar 4 is displaced downwards in order to unclamp the tool holder 2 with the conventional structure, the tool holder 2 is naturally dropped from the spindle 1 by gravity action. For this reason, there is a limitation in use, that is, it is not possible to clamp and unclamp the draw bar 4 unless the tool holder is securely grasped by the tool holder holding mechanism of the tool change arm when changing tools by means of an automatic tool changer, thereby causing such a problem as tools can not be quickly changed, to occur.
OBJECT OF THE INVENTION
The present invention attempts to solve the above problems, and it is therefore an object of the invention to provide a spindle unit by which high precision machining can be made possible by making the clamping force of a tool holder secure and tight without excessively increasing the energy force of the coned disk spring. Also, not excessively increasing the energy force of the coned disk spring can bring easy operation of unclamping and can avoid action of excessive thrust to the bearings of the spindle.
In addition, this spindle unit can prevent a tool holder from dropping from the holder fixing spindle even when the tool change arm does not hold the tool holder in the tool change work, thereby causing the tool holder to be timely clamped and unclamped and the tool change work to be quickly carried out.
Furthermore, as it is possible to clamp and unclamp the tool holder even before the holder fixing spindle stops its revolution completely, a quick tool change work can be much more promoted. These and other objects of the invention will be made apparent in the ensuing description with reference to the drawings attached herewith.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1A is a longitudinal sectional view of a spindle unit for fixing a tool, and FIG. 1B shows an enlarged detailed view of an important part thereof,
FIG. 2 is a longitudinal sectional view of a machining center including the head portion thereof,
FIG. 3 is the plan view of the same machining center,
FIG. 4 is the front elevation view of the same machining center,
FIGS. 5 A and B are an explanation view showing the tool fixing operation, and
FIG. 6 is an explanation view showing a part of the conventional spindle unit.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
In each of the drawings, a table 7 moves longitudinally and laterally on the base 8 of a machining center. A column 9 stands on the base 8 and is provided with guide rails 10 and 10 at the front side thereof. Then, the tool holder fixing spindle 1 is vertically slidably supported by way of the corresponding guide rails 10 and 10.
A spindle head feeding motor 12 is fixed on the surface of the column 9, and the main drive shaft 12a thereof is linked with a screw shaft 13 and a nut member 14 fixed at the spindle head 11 is screwed to the corresponding screw shaft 13, thereby causing the spindle head 11 to be vertically displaced by rotation of the main drive shaft 12a.
And the spindle 1 is rotatably supported at the spindle head 11 in the longitudinal direction by way of bearings 15 and 15. A drive pulley 16 is fixed at the upper part of the spindle 1. To the contrary, the spindle motor 17 is fixed at the spindle head 11. At the same time, a drive pulley 18 is fixed to the main drive shaft 17a thereof, and a power transmission belt 19 are attached to the corresponding pulleys 18 and 16, thereby causing the spindle 1 to rotate by rotation of the main drive shaft 12a. Moreover, an operating hole 1b is provided along with the center axis line of the spindle 1 therein, and a staged portion "b" is formed at the lower tip end portion of the corresponding operating hole 1b and a tapered hole 1a is formed downwards thereof, into which the tapered portion 2a of the tool holder 2 is inserted. Besides, a draw bar 4 is so inserted inwardly of the corresponding operating hole 1b that it can be vertically slidably displaced in a certain range.
Next, the ensuing description explains the internal structure of the spindle 1.
A sleeve 20 having a protrusion flange p formed outwards at the circumferential part of the lower end portion is inserted into the staged portion "m" formed at the lower end portion of the operating hole 1b. At this time, the inner opening 20a of the sleeve 20 is set to such a dimension as the pull stud 2b of the tool holder 2 can be inserted and a plurality of through holes 20b are made in the direction of radius at a position a little upwards of the protrusion flange "p".
The inner opening 20a of the sleeve 20 is so composed as the pull stud 2b can be inserted and the lower surface part of the expansion portion "S" is engaged with the sleeve 20 by way of a ball 6 inserted in the through hole 20b of the sleeve 20, in order to prevent the pull stud 2b from dropping. At this time, the opposite side of the ball 6 is so positioned that it can be brought into contact with the wedge body 21a of the cylindrical body 21 inserted in the inner opening 1b of the spindle 1. Concretely speaking, the cylindrical body 21 is axially mounted from under a staged portion K 1 of the draw bar 4, and the lower end portion of the corresponding body 21 is formed to be a wedge body 21a having L-shaped section faced inwardly and forms an inclination face "g" expanding upwards on the inner circumferential face of the corresponding cylindrical body 21. Then, the wedge body 21a of the corresponding cylindrical body 21 receives repulsion force of the coned disk spring by way of a ring 23, a spring 24, and a sleeve 22. Thus, the repulsion force of the spring is smaller than that of the coned disk spring.
The lower portion of the draw bar 4 is formed to be a slender rod 4c which is narrowed at two staged portions K 1 and K 2 and the coned disk spring 5 is so provided as to cover the slender rod 4c under the staged portion K 2 . At this time, the upper end of the coned disk spring 5 is brought into contact with the staged portion K 2 of the slender rod 4c, and the lower end thereof is brought into contact with a ring 23 provided at the upper surface of the sleeve 20. Thereby, the repulsion force of the coned disk spring 5 operates directly on the sleeve 20 and does on the wedge body 21a of the cylindrical body 21 by way of a spring 24 and another sleeve 22. Also, the lower end of the slender rod 4c of the draw bar 4 passes through the ring 23 and the sleeve 20 and is inserted into the inner opening 20a of the sleeve 20. And as force operating upwards is given to the draw bar 4 by the repulsion force of the coned disk spring 5, the lower end of the slender rod 4c is in non contact with the expansion portion "S" of the pull stud 2b, leaving suitable space between them.
Also, an unclamp bracket 26 is rotatably attached to the upper end of the draw bar 4 by means of bearing 25, thereby causing a push-down force to operate on the upper surface of the corresponding unclamp bracket 26 even while the spindle 1 is in revolution.
Next, a bending type lever 27 is used for vertically moving the draw bar 4 and is axially fixed to the supporting arm 28 which stands from the spindle head, by way of an axis 29. One end of the lever 27 is axially provided with a push bolt 30 and the other end thereof is axially provided with a roller 31. At this time, a stopper 32 stands on the upper surface of the spindle head 11 which is downwards of the lever 27. At the same time, pushing means 34 by a spring 33 is secured at the position opposite to the corresponding stopper 32 between the lever 27 and the spindle head 27, thereby causing the lever 27 which is free to be brought into contact with the stopper 32 and to be maintained at a fixed position. On the other hand, a cam plate 35 is so fixed at the column 9 that it can move and be vertically adjusted. If the spindle head 11 goes upwards more than a fixed height beyond the area of machining, the inclined cam face 35a which is formed on the cam plate 35 pushes and moves the roller 31 only by a fixed distance in an almost horizontal direction. In accompanying therewith, the push bolt 30 pushes down the unclamp force bracket 26 only by a fixed distance.
Also, the tool change arm 36 is fixed at the rotary shaft 38 of the automatic tool changer 37 and a magazine equipment 39 is for accommodating spare tools integral with tool holders 2 thereof.
Next, the ensuing description explains the action for changing tools, using the unit of such a structure as shown in the above.
In machining, the spindle 1 clamps the tool holder 2 at such a condition as shown in FIG. 1 and FIG. 2. However, when changing tools, the spindle head 11 is displaced upwards from the area of machining and the roller 31 of the lever 27 is brought into contact with the cam plate 35 before reaching the tool changing position, thereby causing the draw bar 4 to be pushed down and displaced by vibrations of the lever 27. At this time, as the unclamp force bracket 26 can rotate even though the rotation of the spindle 1 does not come to a complete stop, the draw bar 4 can be pushed down and displaced with any hindrance. And as the draw bar 4 is displaced downwards, the inclination face "g" of the wedge body 21a of the cylindrical body 21 which pushes the outside of the ball 6 is released from the ball 6, thereby causing the positional restriction of the ball 6 to be released. Therefore, the tool holder 2 can be unclamped. (See FIG. 5A). But as the lower end of the sleeve 22 pushes the ball 6 inwardly of the through holes 20 by virtue of the energy force of the spring 24 even under this condition, the pull stud 2b can maintain its controlled and engaged condition by the ball 6, thereby causing the tool holder 2 not to drop by the gravity thereof.
As the spindle head 11 completely reaches the tool change position, the tool change arm 36 turns by 90 degrees around the axis 38 and holds the tool holder 2 at one end grasping portion. At the same time, the tool change arm 36 immediately comes down. Thereby the tool holder 2 is pulled downwards. At this time, the pull stud 2b pushes the ball out of the through hole 20 against the energy force of the spring 24 and the tool holder 2 can be carried out without any hindrance. (See FIG. 5 B). In comparison with the conventional structure in which the tool holder 2 can be unclamped only after the tool change arm 36 holds the tool holder 2, this system disclosed by the present invention can remarkably shorten the tool changing time.
Thereafter, the tool change arm 36 turns by 180° around the axis 38 and locates the tool holder 2 in which a tool to be used next is fixed, right below the spindle 1 for the other end holding portion of the arm 36. Then, the tool change arm 36 elevates the tool holder 2 and insert the corresponding tool holder 2 in the tapered hole 1a of the spindle 1 up to a fixed position. Thereby the pull stud 2b can be repulsively inserted in the inner opening 20a of the sleeve 20, letting the unclamped ball 6 escape outwardly of the through hole 20b against the energy force of the spring 24. Right thereafter, the tool change arm 36 turns reversely by 90° to release the tool holder 2 and returns to the original position thereof. However, as the ball 6 is given the energy force which actuates inwardly of the through holes 20b by the spring 24 and the sleeve 22, as well as mentioned above, engagement of the pull stud 2b can be maintained, thereby causing the tool holder 2 not to drop from the tapered hole 1a of the spindle 1. This also contributes to remarkably shortening the tool change time in comparison with the conventional system in which the tool holder 2 can be unclamped only after the tool change arm 36 holds the tool holder 2, as well as in the above description. And after the tool change arm 36 returns to the original position thereof, the spindle head 11 is lowered to the area of machining again. In the meanwhile, as the roller 31 comes off from the cam plate 35, the lever 27 is made free to cause the draw bar 4 to be released. Thereby the draw bar 4 moves upwards by repulsion force of the coned disk spring 5 and the inclination face "g" of the wedge body 21a forcedly moves the ball 6 inwardly of the through hole 20b. At this time, the inclination face "g" of the wedge body 21a receives a force of the coned disk spring 5 and forcedly moves the ball 6 inwardly of the through hole 20b, thereby causing the ball 6 to be tightly pushed to the lower inclined face of the expansion portion of the pull stud 2b. For this reason, the tool holder 2 is strongly pulled in the tapered hole 1a and is securely and tightly clamped. Thereafter, the spindle 1 is driven and rotate for machining.
According to the present invention, as the clamping force of the tool holder is made secure and strong by the wedging action of the inclination face of the wedge body formed at the lower end of the draw bar, highly precision machining can be permitted. This system does not need any increase of the repulsion force of the coned disk spring unlike the conventional structure. Therefore, the operating force for unclamping can be decreased, and it is possible to avoid that excessive thrust operates on the bearings of the spindle.
Even when the tool change arm does not hold the tool holder in the tool changing work, it is possible to prevent the tool holder from coming off from the holding fixing spindle and timely to clamp and unclamp the tool holder, thereby causing the tool changing work to be quickly carried out.
Furthermore, as it is possible to clamp and unclamp the tool holder under such a condition that the holder fixing spindle does not come to a complete stop, the tool changing work can be carried out very quickly. | The present invention relates to a spindle unit of a machine tool in which tools changing is available and especially relates to a spindle unit by which a tool in a tool holder can be quickly and safely clamped and unclamped. This spindle unit is characterized in that an operating hole along with the centerline axis of a rotary spindle is provided therein for fixing (or clamping) a tool, a draw bar furnished with a cylindrical body along with the inner circumferential face of the operating hole is provided therein, the lower portion of the cylindrical body is formed on the inclination face of a wedge body, and a tool is clamped by guiding a ball by which the pull stud of a tool holder is engaged, along with the inclination of the inclination face of the wedge body, that is, by movement of the ball toward the center of the spindle, and is unclamped by the reverse movement of the ball. | 8 |
CROSS-REFERENCE TO RELATED APPLICATIONS
[0001] Not Applicable
STATEMENT REGARDING FEDERALLY SPONSORED RESEARCH
[0002] Not Applicable
FIELD OF THE INVENTION
[0003] The invention relates to a press for producing a pellet from powdered material, comprising a press frame and a press unit arranged in the press frame with at least one upper press punch and/or at least one lower press punch, as well as at least one receptacle for the powdered material to be pressed by the upper and/or lower press punch, at least two upper drive units, each with one upper electric drive motor for moving the upper press punch in a vertical direction, wherein the upper drive units each comprise one upper spindle drive driven by the respective electric drive motor and having an upper spindle and an upper spindle nut, and/or at least two lower drive units, each with a lower electric drive motor for moving the lower press punch and/or the receptacle in a vertical direction, wherein the lower drive units each comprise a lower spindle drive driven by the respective electric drive motor and having a lower spindle and a lower spindle nut, wherein the upper drive units act laterally offset on the at least one upper press punch by means of an upper power transmission bridge extending in a horizontal direction, and/or wherein the lower drive units act laterally offset on the at least one lower press punch and/or the receptacle by means of a lower power transmission bridge extending in a horizontal direction.
BACKGROUND OF THE INVENTION
[0004] A press for producing a pellet from powdered material is for example known from EP 2 479 022 A1, the entire contents of which are hereby incorporated by reference. Flexible connecting means are provided for example between an intermediate element connected to two parallel drive means acting along the vertical axis and the drive means. Furthermore, flexible connecting means can be provided between the intermediate element and a die plate or another intermediate element. Misalignments of parts that can be moved and guided along the vertical axis of the press are avoided by the flexible connecting means. In particular, a largely synchronous traveling movement of the drives is achieved.
[0005] The unpublished, parallel German patent application 10 2012 010 767.6, the entire contents of which are hereby incorporated by reference, by the applicant furthermore proposes arranging spring elements that, during a pressing operation, deform between the power transmission bridges acted upon by the drive units in a laterally offset manner, and the drive units. The drive units can in particular comprise spindle drives with spindles and spindle nuts. The spring elements largely minimize the influences on the pressing result from bending press components. In particular, bending moments acting on the spindle nuts are reduced.
[0006] In the operation of presses of the above-described type, significant bending moments act on drive components, in particular any spindle drives that may be provided. This holds true in particular when the drives act on opposite sides of a power transmission bridge extending in a horizontal direction. Given the enormous press forces, the power transmission bridges can significantly bend and thereby generate the noted bending moment. This problem is not solved, or is at least not completely solved, by the spring elements provided in the prior art.
BRIEF SUMMARY OF THE INVENTION
[0007] Proceeding from the prior art, the object of the invention is therefore to provide a press of the initially-cited type in which the effects of bending moments on the drives are further minimized during pressing.
[0008] The invention achieves this object through the subject disclosed herein. Advantageous embodiments can be found in the description and the figures.
[0009] The invention achieves the object for a press of the initially-cited type in that the upper spindle nuts, or the upper fastening elements each connected to the upper spindle nuts, are each connected to the upper power transmission bridge by at least one upper compensation element, wherein the compensation elements are each rotatably mounted on the upper spindle nuts, or the upper fastening elements on the one hand, and on the upper power transmission bridge on the other hand, and/or that the lower spindle nuts, or lower fastening elements connected to the lower spindle nuts, are each connected to the lower power transmission bridge by means of at least one lower compensation element, wherein the compensation elements are each rotatably mounted on the lower spindle nuts, or the lower fastening elements on the one hand and the lower power transmission bridge on the other hand.
[0010] The press according to the invention possesses a press frame that stands on feet or directly on the supporting surface. A press unit is arranged in the press frame and has at least one upper press punch and/or at least one lower press punch. This press unit furthermore possesses a receptacle in which powder to be pressed is added before pressing by the press punch(es).
[0011] The powdered material can for example be a metal or ceramic powder. The receptacle is arranged between the upper punch and the lower punch. Generally, the press comprises at least one upper and at least one lower punch that interact in the receptacle for pressing the added powder. It is, however, also conceivable to press for example only from above with only one upper punch when the receptacle has a closed floor.
[0012] The upper and/or lower press punches can be arranged on an upper or respectively lower punch plate. To vertically move the upper and/or lower punch during the pressing process, upper and/or lower drive units are provided that have upper and/or lower electric drive motors. In particular, at least two upper drive units and at least two lower drive units are provided. The upper or respectively lower drive units can be arranged symmetrically on opposite sides of the press frame. As explained, the lower drive units drive a lower press punch or a receptacle in a vertical direction. Operating the press is feasible both in an ejection process in which the receptacle is stationary and the upper and lower punches are moved relative to the receptacle, as well as in a withdrawal process in which the lower punch is stationary, and the receptacle as well as the upper punch are movable. In principle, the number of press axes and hence the simultaneously created pellets can be increased within broad limits with the press according to the invention. The press unit can form a module that is removed as a whole from the press and can be exchanged with another press unit also forming a module. The receptacle can be formed in a die plate. It can be securely arranged on the press frame.
[0013] The upper drive units act laterally offset on the at least one upper press punch by means of an e.g. bar-shaped upper power transmission bridge. Correspondingly, the lower drive units act laterally offset on the at least one lower press punch and/or the receptacle by means of the e.g. bar-shaped lower power transmission bridge. Thus, the drive units act off-center on the press punch, or respectively the receptacle. The direction of movement (or respectively direction of force) of the drive units is generally spaced parallel from the direction of movement (or respectively direction of force) of the upper punch and the lower punch, or respectively the receptacle. The drive units therefore act on the press unit in a non-coaxial manner. The power transmission bridges can for example be connected in the middle to the upper press punch, or respectively an upper punch plate bearing the upper press punch, or respectively to the lower press punch, or respectively a lower punch plate bearing the lower press punch, or the receptacle. At least one additional power transmission element can be provided between each of the power transmission bridges and the press punches, or respectively the receptacle. Of course, more than two, for example four upper, and/or more than two, for example four lower drive units, can in principle be provided. In this case, two drive units each can act on one end of the respective power transmission bridge.
[0014] The two upper, or respectively two lower drive units, act synchronously on the upper, or respectively lower, power transmission bridge. The upper or respectively lower drive units furthermore each comprise an upper or respectively lower spindle drive driven by the upper or respectively lower drive motor and having an upper or respectively lower spindle and an upper or respectively lower spindle nut. The upper or respectively lower spindle nuts are each connected to the upper or respectively lower power transmission bridge such that the upper or respectively lower power transmission bridge is moved together with the respective spindle nuts in an axial direction when the spindles are moved in the spindle nuts.
[0015] The force exerted by the drive units is transferred to the press unit by means of the respective power transmission bridge. Due to the offset acting of the drive units, the power transmission bridges can bend due to the very high force that can arise during the pressing process which, in the prior art, can lead to bending moments being applied to the spindle nuts and hence to an impairment of the functioning of the spindle drive. To solve this problem, the invention provides that the upper or respectively lower spindle nuts, or upper or respectively lower fastening elements connected to the upper or respectively lower spindle nuts, are each connected to the upper or respectively lower power transmission bridge by at least one upper or respectively lower compensation element. The compensation elements are, on the one hand, rotatably mounted to the upper or respectively the lower spindle nuts, or the upper or respectively the lower fastening elements. On the other hand, the compensation elements are rotatably mounted to the upper or respectively lower power transmission bridge. The compensation elements establish in particular the exclusive connection between the spindle nuts, or respectively the fastening elements, and the respective power transmission bridge.
[0016] The compensation elements can possess an elongated shape, and its opposite ends can then be rotatably mounted to the respective power transmission bridge on the one hand and the respective spindle nut, or respectively the respective fastening element, on the other hand. The compensation elements accordingly form a double joint. The power transmission bridges in combination with at least two double joints in each case further reduce transmission of bending moments to the spindle drives, in particular to the spindle nuts, in comparison to the prior art. Each shortening of the power transmission bridge due to bending, and hence a shortening of the distance between the bearing points of the compensation elements on the power transmission bridges, is compensated by a rotation of the compensation elements about the bearing points. The bending moments arising from a bending of the power transmission bridges is hence not transferred to the spindle drives, in particular to the spindle nuts.
[0017] Following the release after the end of the pressing process, the components move back into their initial position. Remaining force and moments applied to the spindle nuts only result from oblique force vectors/transverse forces as well as the friction moment of the pivot bearings. The compensation elements according to the invention are substantially non-flexible. In contrast to the prior art, no flexible elements are required; rather, tipping moment is compensated by the tilting of the compensation elements enabled by the pivot bearings.
[0018] The spindle drives generate torque, in particular opposing torque, that can act by means of the compensation elements on the first transmission bridge. Such torque is fundamentally undesirable. Consequently, a torque support or respectively anti-rotation element can be provided that prevents a transmission of torque to the power transmission bridges, yet however permits a deflection of the power transmission bridges. For example, a stiffening plate that is connected, e.g. screwed, to each spindle nut and e.g. can be arranged in a horizontal plane, has proven to be suitable in practice. The stiffening plate can be connected, e.g. also screwed, to the power transmission bridge by means of one or more support elements.
[0019] As mentioned, the compensation elements can either be rotatably mounted to the spindle nuts or to fastening elements connected to the spindle nuts. Such fastening elements are optional. Like the spindle nuts, they can be designed disk- or ring-shaped and can be arranged between a respective spindle nut and the respective power transmission bridge. It is, however, also possible for the spindle nuts to be arranged between such a fastening element and the respective power transmission bridge.
[0020] According to one embodiment, each of the upper spindle nuts, or respectively each upper fastening element connected to the upper spindle nuts, can be connected in each case to the upper power transmission bridge by two upper compensation elements, and/or each of the lower spindle nuts or respectively each lower fastening element connected to the lower spindle nuts, is connected in each case by two lower compensation elements to the lower power transmission bridge. The compensation elements can each be arranged upon opposing sides of the power transmission bridge. The compensating effect is further optimized by providing four compensation elements per power transmission bridge.
[0021] The bearing points for rotatably mounting the compensation elements can always be arranged over each other in a vertical direction when the press is in a state of rest, that is, before a pressing operation. The compensation elements are rotatably mounted to sections of the respective power transmission bridges arranged vertically over each other, and the respective spindle nuts, or respectively fastening elements. If the power transmission bridges bend during pressing, the compensation elements tip so that the bearing points are then arranged along a line running at an angle to the vertical. A particularly even compensating effect arises.
[0022] In principle, any type of pivot bearing is conceivable for the compensation elements. For example, the compensation elements can be rotatably mounted by roller bearings or friction bearings. The pivot bearings can each comprise bearing pins that are attached to the respective power transmission bridge and the respective spindle nuts, or respectively to the respective fastening element. Bearings corresponding to the bearing pins can then be provided on the compensation elements. A kinematic reversal is, however, also possible in which the bearing ends are formed on the compensation elements, and the bearings are correspondingly formed on the power transmission bridges and the spindle nuts, or respectively fastening elements.
[0023] Furthermore, the at least two upper drive units can act on the opposite ends of the upper power transmission bridge. Correspondingly, the at least two lower drive units can act on the opposite ends of the lower power transmission bridge. This embodiment is particularly suitable for the pressing operation. On the other hand, a particularly high bending moments act on the power transmission bridge that, however, can be reliably compensated according to the invention by the compensation elements.
[0024] It can be provided according to another embodiment that the upper spindles, and/or the upper spindle nuts, and/or the upper fastening elements do not touch the upper power transmission bridge when the press is in a state of rest and during a pressing operation, and/or the lower spindles, and/or the lower spindle nuts, and/or the lower fastening elements do not touch the lower power transmission bridge when the press is in a state of rest and during a pressing operation. According to this embodiment, the respective power transmission bridge can bend at least up to a certain limit without the power transmission bridge coming into direct contact with the spindle and/or its neighboring spindle nut, or respectively with its neighboring fastening element if available. Such a contact would cause a transmission of the bending moments to the spindle nut and hence possibly cause the spindle drives to tip. With a suitable constructive embodiment of the press components, the addressed limit to the bending of the respective power transmission bridge can be selected so that there is no undesirable contacting of the components and hence tipping moment exerted on the spindle drives also during the force arising in the context of a pressing operation.
[0025] A space can be formed between a bottom side or a top side of the upper power transmission bridge and a top side, or respectively a bottom side of the upper spindle nuts, or respectively the upper fastening elements, and/or a space can be formed between a bottom side or a top side of the lower power transmission bridge and a top side, or respectively a bottom side of the lower spindle nuts, or respectively the lower fastening elements. The space is formed between the components directly neighboring the power transmission bridge. As explained above, this can be the respective spindle nut. It can, however, be a fastening element connected to the spindle nut.
[0026] According to another embodiment, each of the opposite ends of the upper power transmission bridge can possess a cylindrical through-hole, each of which accommodates an upper spindle, wherein an annular gap is formed in each case between the insides of the through-holes in the upper power transmission bridge and the outsides of the upper spindles, and/or each of the opposite ends of the lower power transmission bridge possesses a cylindrical through-hole, each of which accommodates a lower spindle, wherein an annular gap is formed in each case between the insides of the through-holes in the lower power transmission bridge and the outsides of the lower spindles.
[0027] According to an alternative embodiment in this regard, a cylindrical upper projection is connected to each of the upper spindle nuts, wherein each of the opposite ends of the upper power transmission bridge can possess a cylindrical through-hole, each of which accommodates an upper projection, wherein an annular gap is formed in each case between the insides of the through-holes in the upper power transmission bridge and the outsides of the upper projections, and/or a cylindrical lower projection is connected to each of the lower spindle nuts, wherein each of the opposite ends of the lower power transmission bridge possesses a cylindrical through-hole, each of which accommodates a lower projection, wherein an annular gap is formed in each case between the insides of the through-holes in the lower power transmission bridge and the outsides of the lower projections.
[0028] In the two last-cited embodiments, the ends of the power transmission bridges each form bearing sections with cylindrical through-holes. The diameters of the cylindrical through-holes in these embodiments are greater by a specific value than the diameters of the (cylindrical) spindles, or respectively the cylindrical projections of the spindle nuts. This forms the annular gap.
[0029] In the aforementioned embodiments, spaces run around the spindles, or respectively the projections of the spindle nuts, and between the spindle nuts or respectively the fastening elements and the power transmission bridges. These are particularly practical embodiments for reliably avoiding the aforementioned contacts during operation. The gaps or respectively spaces can be selected to be correspondingly large enough so that a maximum bending of the power transmission bridge arising during pressing does not yield undesirable contact and hence tipping moment exerted on the spindle drives. The spaces between the power transmission bridges and the spindle nuts, or respectively the fastening elements, can for example possess a width of 1 to 10 mm, preferably 2 to 5 mm. Correspondingly, the annular gap between the spindles, or respectively the cylindrical projections on the spindle nuts, and the cylindrical through-holes in the power transmission bridges can possess a width of 1 to 10 mm, preferably 2 to 5 mm.
[0030] According to another particularly practical embodiment, the press frame can have an upper and a lower holding plate that are connected by a plurality of vertical spacers. This yields particularly high stability. The drive motors of the upper drive units can furthermore be fastened to the upper holding plate of the press frame, and the drive motors of the lower drive units can be fastened to the lower holding plate of the press frame. The drive motors are therefore arranged on the press frame such that they are not entrained during a vertical movement of the press punch, or respectively the receptacle. This increases the stability and improves the result of pressing. A bearing element can be provided that is arranged on the vertical spacers of the press frame between the upper and lower holding plate of the press frame. The bearing element can, for example, to be designed as a single piece. The receptacle can be arranged on the bearing element. As mentioned, the receptacle can be formed in a die plate. The die plate can be formed separate from the bearing element and, for example, be fastened to the bearing element. The upper and lower punch can then move relative to the bearing elements and hence to the die plate with the receptacle. For particularly high stability, the bearing element can possess a U-shape that lies in a plane oriented perpendicular to the longitudinal axis of the press frame, in particular a horizontal plane.
BRIEF DESCRIPTION OF THE DRAWINGS
[0031] Exemplary embodiments of the invention are explained below in greater detail with reference to figures. They show schematically:
[0032] FIG. 1 A perspective view of a press according to the invention,
[0033] FIG. 2 A detail of the press shown in FIG. 1 in a first operating state,
[0034] FIG. 3 The detail from FIG. 2 in a second operating state,
[0035] FIG. 4 A representation of an enlarged section of a part of the representation from FIG. 2 .
DETAILED DESCRIPTION OF THE INVENTION
[0036] While this invention may be embodied in many forms, there are described in detail herein specific embodiments of the invention. This description is an exemplification of the principles of the invention and is not intended to limit the invention to the particular embodiments illustrated.
[0037] If not otherwise specified, the same reference numbers indicate the same objects in the figures. The press according to the invention possesses a press frame 10 with an upper holding plate 12 and a lower holding plate 14 . The upper and lower holding plates 12 , 14 are connected to each other by means of four spacers 16 running in a vertical direction in the portrayed example, and to a bearing element 18 arranged approximately in the middle between the upper and lower holding plates 12 , 14 . In the portrayed example, the bearing element 18 is designed as a single part and possesses a U-profile lying in a horizontal plane, an arrangement and extension plane. The lower holding plate 14 stands on the supporting surface by means of four support legs 20 . Furthermore, the press possesses an upper punch plate 22 with an upper punch (not shown) and a lower punch plate 24 with a lower punch (also not shown). In the portrayed example, a die plate 26 is arranged between the upper punch plate 22 and the lower punch plate 24 with a receptacle (not shown) for powder to be pressed between the upper and lower punch, such as metal or ceramic powder. In the portrayed example, the upper punch plate 22 , the lower punch plate 24 , and the die plate 26 are connected to each other by means of vertical guide columns 28 . In the portrayed example, the die plate 26 is directly attached to the bearing element 18 .
[0038] The press according to the invention furthermore comprises two upper drive units for vertically moving the upper punch plate 22 , and two lower drive units for vertically moving the lower punch plate 24 . The upper and lower drive units are each arranged on opposite sides of the press frame 10 . The upper drive units comprise in each case an upper electric drive motor 30 , 31 arranged on the upper holding plate 12 and an upper spindle drive. The upper spindle drives comprise in each case an upper fixed bearing 32 , 33 that is fastened in each case directly to the top side of the bearing element 18 . The electric upper drive motors 30 , 31 each rotatably drive an axially fixed upper spindle 34 , 35 . An upper axially movable upper spindle nut 36 , 37 is arranged on each of the upper spindles 34 , 35 . When the upper spindles 34 , 35 rotate, this therefore generates an axial movement of the respective upper spindle nuts 36 , 37 . In a manner explained further below, the upper spindle nuts 36 , 37 are fastened to opposite ends of an upper, bar-shaped power transmission bridge 38 which is connected in the middle to the upper punch plate 22 by means of another power transmission element 40 . The upper drive units with their upper drive motors 30 , 31 therefore act laterally offset on the upper punch plate 22 and hence on the upper punch by means of the power transmission bridge 38 .
[0039] The design of the two bottom drive units is accordingly identical to the design of the two upper drive units. Accordingly, the lower drive units each have a lower electric drive motor 42 , 43 that is arranged on the lower holding plate 14 and rotatably drives an axially fixed lower spindle 44 , 45 . A lower fixed bearing 46 , 47 of each of the lower spindles 44 , 45 is directly fastened to the bottom side of the bearing element 18 . An axially movable lower spindle nut 50 , 51 is in turn arranged on the lower spindles 44 , 45 . The lower spindle nuts 50 , 51 are in turn arranged on opposite ends of a lower, bar-shaped power transmission bridge 52 which is connected in the middle to the lower punch plate 24 by means of another power transmission element 54 . When the lower electric drive motors 42 , 43 rotatably drive the lower spindles 44 , 45 , an axial movement of the lower spindle nuts 50 , 51 arises which, in a manner yet to be explained, is transmitted to the lower punch plate 24 by means of the lower power transmission bridge 52 and the power transmission element 54 such that the punch plate is moved in a vertical direction. In turn, the lower drive units with their lower drive motors 42 , 43 therefore act laterally offset on the lower punch plate 24 and hence on the lower punch by means of the lower power transmission bridge 52 .
[0040] In the depicted example, the upper spindle nuts 36 , 37 are connected to the upper power transmission bridge 38 by means of a total of four compensation elements, of which two can be seen in FIG. 1 under reference numbers 56 , 58 . Corresponding compensation elements with an equivalent function are arranged on the rear of the press, hidden in FIG. 1 , opposite the compensation elements 56 , 58 in each case. The lower spindle nuts 50 , 51 are correspondingly connected by means of a total of four compensation elements to the lower power transmission bridge 52 , of which two can be seen in FIG. 1 under reference numbers 60 , 62 . On the other hand, on the rear of the press which cannot be seen in FIG. 1 , there are two additional compensation elements opposite compensation elements 60 , 62 which are identical to the compensation elements 60 , 62 in terms of design and function.
[0041] The elongated compensation elements 56 , 58 , 60 , 62 are each rotatably mounted on the upper power transmission bridge 38 , or respectively the lower power transmission bridge 52 , by means of first pivot bearings 64 , 66 , 68 , 70 in each case. The compensation elements 56 , 58 , 60 , 62 are each rotatably mounted on the upper, or respectively lower spindle nuts by means of second pivot bearings 72 , 74 , 76 , 78 . It can be seen that the pivot bearings of a compensation element in the rest position of the press shown in FIG. 1 are each arranged over each other in a vertical direction. The longitudinal axis of the elongated compensation elements 56 , 58 , 60 , 62 also extends in a vertical direction in this state of rest.
[0042] The function of the compensation elements will be explained as an example in relation to the upper power transmission bridge 38 with reference to FIGS. 2 and 3 . Of course, the function of the compensation elements in relation to the lower power transmission bridge 52 is accordingly identical. As in FIG. 1 , the state of rest of the press in the section from FIG. 1 is shown in FIG. 2 . During a pressing operation, enormous forces arise. These can cause the power transmission bridges 38 , 52 to bend as exaggeratedly depicted in FIG. 3 for the sake of illustration with reference to power transmission bridge 38 . As can be seen in FIG. 3 , this bending of the power transmission bridge 38 leads to a tipping of the compensation elements 56 , 58 which is enabled by a rotation about the pivot bearings 64 , 72 , or respectively 66 , 74 . The distance decreases between the pivot bearings 64 , 66 relative to each other that are provided on the power transmission bridge 38 , whereas the distance between the pivot bearings 72 , 74 remains substantially constant. As can also be seen in FIGS. 2 and 3 , a space exists between the top side of the spindle nuts 36 , 37 and the assigned bottom side of the upper power transmission bridge 38 which is sufficiently large so that no direct contact arises between the spindle nuts 36 , 37 and the power transmission bridge 38 during the bending depicted in FIG. 3 . It can also be seen that the spindles 34 , 35 are accommodated in through-holes that in turn are formed in bearing sections at opposite ends of the power transmission bridge 38 . The outer diameter of the spindles 34 , 35 is less by a specific amount than the inner diameter of the through-holes in the power transmission bridge 38 . Consequently, there is an annular gap between the outside of the spindles 34 , 35 and the inside of the through-holes in the power transmission bridge 38 . This annular gap is also sufficiently large so that direct contact of the spindles with the power transmission bridge 38 does not arise in the state shown in FIG. 3 . Of course, the embodiment of the lower part of the press shown in FIG. 1 , in particular the connection between the spindle drives and the power transmission bridge 52 , is accordingly identical. The aforementioned embodiments with the compensation elements 56 , 58 , 60 , 62 ensure that no relevant bending moments act on the spindle drives, in particular the spindle nuts 36 , 37 , 50 , 51 .
[0043] Furthermore, a torque support, or respectively anti-rotation element of the press according to the invention can be seen in the figures, in particular the enlarged representation in FIG. 4 . It comprises a reinforcing plate 76 screwed to each of spindle nuts 36 , 37 , 50 , 51 which in the present case is arranged in a horizontal plane. The corresponding screwed connections can be seen under reference sign 79 . In the portrayed example, the stiffening plate 76 is screwed to the power transmission bridge 38 by means of two support elements 80 . The corresponding screwed connections can be seen under reference sign 82 . The torque support secures against undesirable twisting. Of course, corresponding torque supports, or respectively anti-twist elements, are provided on all the spindle nuts 36 , 37 , 50 , 51 .
[0044] The above disclosure is intended to be illustrative and not exhaustive. This description will suggest many variations and alternatives to one of ordinary skill in this art. All these alternatives and variations are intended to be included within the scope of the claims where the term “comprising” means “including, but not limited to”. Those familiar with the art may recognize other equivalents to the specific embodiments described herein which equivalents are also intended to be encompassed by the claims.
[0045] Further, the particular features presented in the dependent claims can be combined with each other in other manners within the scope of the invention such that the invention should be recognized as also specifically directed to other embodiments having any other possible combination of the features of the dependent claims. For instance, for purposes of claim publication, any dependent claim which follows should be taken as alternatively written in a multiple dependent form from all prior claims which possess all antecedents referenced in such dependent claim if such multiple dependent format is an accepted format within the jurisdiction (e.g. each claim depending directly from claim 1 should be alternatively taken as depending from all previous claims). In jurisdictions where multiple dependent claim formats are restricted, the following dependent claims should each be also taken as alternatively written in each singly dependent claim format which creates a dependency from a prior antecedent-possessing claim other than the specific claim listed in such dependent claim below.
[0046] This completes the description of the preferred and alternate embodiments of the invention. Those skilled in the art may recognize other equivalents to the specific embodiment described herein which equivalents are intended to be encompassed by the claims attached hereto. | The invention relates to a press for producing a pellet from powdered material, comprising a press frame and a press unit arranged in the press frame with at least one upper press punch and/or at least one lower press punch, as well as at least one receptacle for the powdered material to be pressed by the upper and/or lower press punch, at least two upper drive units, each with one upper electric drive motor for moving the upper press punch in a vertical direction. | 1 |
This is a division of application Ser. No. 08/157,641, filed Nov. 24, 1993, now U.S. Pat. No. 5,432,456, issued Jul. 11, 1995.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to apparatus and methods for testing printed circuit boards. More particularly, the present invention relates to apparatus and methods for checking all pins of through-hole components after installation to a printed circuit board to ensure that each pin protrudes therethrough sufficiently to allow soldering.
2. Description of Related Art
A wide variety of electronic devices employ printed circuit boards (PCBs). PCBs are boards for the mounting of components on which most connections are made by printed circuitry. Printed circuits (or soldered connections) are, in turn, printed wiring formed in a predetermined design in, or attached to, the surface or surfaces of a common base.
One example of a PCB is a computer motherboard. A computer motherboard is a generally rectangular component, made of plastic and strips of metal, designed to house a central processing unit (CPU) and related integrated circuits (ICs). Sockets are built into the surface of the motherboard, designed to hold the legs of the ICs. The legs, or pins, of the ICs are made of a stiff metal and they plug into IC sockets in much the same way electrical plugs slide into wall sockets.
Developments in the electronic arts have heretofore been driven in large part by a desire for components to do more while occupying less space. With respect to PCBs, this desire has caused more and more components, each with a large quantity of delicate pins, to be positioned on those boards in close proximity to each other. It is now not uncommon for a PCB to have over 1500 leads.
Notwithstanding the increased complexity caused by having more and more components attached closely together on a board, it has been and remains an important goal of PCB manufacturers to reduce, if not eliminate, defects.
Towards this goal, apparatus and methods for testing PCBs being manufactured have heretofore been developed.
One important requirement subject to testing is whether each pin of a through-hole component protrudes sufficiently through the PCB. It is important that all pins do so protrude so that good electrical contacts can be made during subsequent soldering processes. This test needs to be accurate because it is difficult to replace components once actually soldered, in whole or in part, to a board.
A prior art method of determining whether each pin of a through-hole component protrudes sufficiently through a PCB is visual inspection. During such an inspection, a board on an assembly line is picked up, turned over, and each through-hole visually checked to see if a pin is protruding through it.
The visual inspection method of testing PCBs has several defects. First, it requires considerable handling of the board, which can cause damage to delicate components. Second, the visual inspection method is time consuming. It can take quite a bit of time for a person to ensure 1,500 or more pins are protruding as required. Additionally, the visual inspection method is unreliable. Because many small delicate pins are often oriented in close proximity to each other, it is easy to miss the fact that one or more are missing or otherwise not protruding as they should.
A second method of checking all pins of through-hole components after installation to a PCB involves performance of an electrical continuity test. This test is directed to ensuring electrical continuity exists between the internal contacts of components above or on one side of the PCB and their corresponding pins below or on the other side of the PCB. Like the visual inspection test, the electrical continuity test has shortcomings and deficiencies. First, although this test can be performed in various ways, each involves physical contact with pins, which can damage them. Second, because the test does require that delicate contacts be made, which is inherently a time consuming process, performing this test increases PCB manufacturing time significantly. Third, it is not uncommon for internal contacts of components to be damaged during this test, which is wasteful and expensive.
Based upon the foregoing, those skilled in the art should understand and appreciate that it is a shortcoming and deficiency of the prior art that there has not yet been developed a quick, highly reliable, nonphysical-contact method for ensuring component pins protrude through a PCB enough to enable soldering.
SUMMARY OF THE INVENTION
The present invention overcomes the shortcoming and deficiency mentioned above by providing a pin protrusion test fixture including an element having a void therethrough, structure for biasing the aforementioned element in a first direction to a first position, and structure for directing a pin toward that element so that the pin causes the element to move in a second direction to a second position. A fixture according to the teachings of the present invention also includes a light source and a light sensor disposed so that light from the light source passes through the void in the element having a void therethrough, whereupon that light can be detected by the light sensor when the element is in the second position.
In an embodiment of the present invention there are a plurality of elements having a void therethrough, structure for biasing each of the plurality of elements, and structure for directing individual pins towards individual elements. In such an embodiment of the present invention, the voids in the elements having a void therethrough may align in at least one line when each of the elements having a void therethrough are in the second position.
In embodiments of the present invention wherein the voids in the elements having voids therethrough align in more than one line when each of the elements having a void therethrough are in the second position, there may also be structure for changing the direction of the light emitted by the light source so that it can travel through all of the voids notwithstanding the fact that they align so as to form more than one line. In embodiments of the present invention, prisms can perform the light beam direction changing function.
Further, according to the teachings of the present invention, optical fibers may be incorporated into embodiments of the present invention to facilitate light travel and control.
Accordingly, it is an object of the present invention to provide a manual assembly fixture that can perform a pin protrusion test without changing the existing assembly process.
Another object of the present invention is to provide a test fixture that can perform a pin protrusion test quickly and accurately.
Yet another object of the present invention is to provide a test fixture that can perform a pin protrusion test without inducing damage.
BRIEF DESCRIPTION OF THE DRAWINGS
Other objects, advantages, and novel features of the present invention will become apparent from the following detailed description of the invention when taken in conjunction with the accompanying drawings wherein:
FIG. 1 is an elevated, partially cut away view of a pin protrusion test fixture according to the teachings of the present invention;
FIG. 2 is an exploded view of a portion of the test fixture depicted in FIG. 1; and
FIG. 3 is a schematic diagram showing how light could travel through an embodiment of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to the drawings wherein like or similar elements are depicted with identical reference numerals throughout the several views, and wherein the various components depicted are not necessarily drawn to scale, and, more particularly, to FIG. 1, there is shown an elevated, partially cut away view of a pin protrusion test fixture (generally designated by reference numeral 10) according to the teachings of the present invention. The fixture 10 may be seen in FIG. 1 to comprise a base plate 12, a test module 14, a means for supplying power 16, and a photoelectric sensor 18. Each of these components is discussed in further detail immediately below.
The base plate 12 serves as a mounting surface for the module 14 and sensor 18. The base plate 12 also serves to support tooling pins 20, 22, 24 on which a PCB 26 may be positioned (via holes 28 therethrough) in a manner so that connector through-holes 30 in the PCB 26 are aligned with holes 32 (discussed further below) in the test module 14. The base plate 12 may be formed by any one of a number of conventional materials (e.g., metal, plastic, or a combination thereof) in conventional ways. It is important, however, that the base plate 12 and tooling pins 20 be strong enough to support elements mounted or positioned thereon and to withstand repeated use. It is also important that the materials used to form the base plate 12 and tooling pins 20 not damage or interfere in any way with the testing of the PCB 26.
The test module 14 can be better seen in FIG. 2. The module 14 shown in FIG. 2 may be seen to comprise a housing 34, a partition block 36, shutter plates 38, compression springs 40, plungers 42, prisms 44, 46 and a cover plate 48. The springs 40, shutter plates 38 and plungers 42 are serially contained in spaces in the partition block 36. A spring 40, shutter plate 38, and plunger 42 unit effectively creates an individual test cell for a component pin.
These "cells" are aligned in parallel rows by the partition block 36 to match the pin pattern of the component being tested. The entire cell and partition block 36 structure is enclosed with the housing 34 and the cover plate 48. Screw holes 50, 52 in the cover plate 48 and housing 34, respectively, provide a means whereby the test module 14 can be stably assembled.
As previously mentioned, the cover plate has holes 32 therethrough aligned with the holes 30 in the PCB. The purpose of holes 30 and 32 are to accept the pins of a through-hole component (e.g., component 54 depicted in FIG. 1) to be soldered to the PCB 26.
When the component 54 is mounted onto the PCB 26, its pins 56 project through the holes 30 and the holes 32, whereupon they impinge upon a plunger 42, shutter plate 38, and spring 40 assembly contained in a particular block cell. Assuming that all of the plungers are depressed simultaneously to the same depth (which should happen if all pins are present and uniform), the shutter plates 38 will align and effectively create a "light window". If, on the other hand, any one plunger is not depressed, a complete, unobstructed light window will not be created.
The purpose of the photoelectric sensor 18 (depicted in FIG. 1) is to determine whether an unobstructed light window exists. The sensor 18 accomplishes this by transmitting light into the test module 14. This can be accomplished by a fiber optic line 58. The sensor 18 may include means (e.g., light emitting diodes) for indicating to a fixture operator whether a light window is created. This possible aspect of an embodiment of the present invention is discussed further below.
Referring now to FIG. 3, there is shown the path of light through an unobstructed module 14. The light enters the module 14 at point 60 and passes through a first "light window" row (the topmost row in FIG. 3) if possible (i.e., if all shutter plates are aligned with the shutter voids on a light beam axis). At the end of this first row, the direction of the light beam is changed by a first prism 62 (or, with reference to FIG. 2, a prism 44) so that the beam reverses direction and travels down a second row (the bottommost row in FIG. 3). At the end of that row, a second, smaller prism 64 (or, again with reference to FIG. 2, a prism 46) again changes the direction of the light beam so that it travels down a third row. Similarly, the light beam may once again be modified by the first prism 62 so that the beam travels down a fourth and last row to a test module exit point 66. Referring to FIG. 1, the light, if any, exiting the test module 14 is carried via fiber optic line 68 to the sensor 18 whereupon its receipt may be detected and subsequently indicated to a test operator. Line 16 provides power to the sensor 18. If a single pin is missing, light will not be able to pass through the test module 14 and the absence of light will be noted by the sensor 18.
Based upon the foregoing, those skilled in the art should understand and appreciate how the present invention may be used. A test operator can place a PCB 26 on the tooling pins 20 and then install a through-hole component 54. The operator can then be prompted immediately by a green light emitting diode (LED) 70 or a red/green LED 72 on the sensor 18 as to whether all pins are present and the component connector is a "go" or as to whether one or more pins is missing and the component connection is a "no go", respectively.
Those skilled in the art should also understand that an embodiment of the present invention has heretofore been made and used with remarkably good results. Details recording this embodiment are set forth below:
______________________________________Springs: OD: .057 inch Length: .320 inch Rating: 1 oz per inch of travelPlunger and Aperture: Formed of Stainless SteelPhotocell: Keyence FS2-62Fiber Optic Cable: 21/2 mm diameter______________________________________
The present invention provides a multitude of advantages over the prior art. The fixture can test component pins as the components are installed without changing the existing process. The operator can replace a defective part immediately prior to soldering. Use of the present invention eliminates time consuming rework of high pin count through-hole components. The present invention improves quality by testing components that are not tested by prior art means.
In addition to the foregoing, the fixture doubles as a PCB support plate. Such plates are commonly used at manual assembly points in assembly lines for through-hole components. Further, the fixture modules and sensors can be reused on new fixtures. Therefore, the cost of new fixtures can be reduced considerably.
Still further, the present invention offers the tremendous advantage of failing correctly. This ensures high result accuracy.
Obviously, numerous modifications and variations are possible in view of the teachings herein. For example, it would be possible and may even be advisable in certain applications to use an integrated plunger and aperture. Embodiments of the present invention could also include an adjustable mount for the light or means for shimming the cover plate to compensate for varying lead lengths. Other modifications and variations are possible. Accordingly, within the scope of the appended claims, the present invention may be practiced otherwise than as specifically described hereinabove. | A pin protrusion test fixture includes an element having a void therethrough, structure for biasing the aforementioned element in a first direction to a first position, and structure for directing a pin toward that element so that the pin causes the element to move in a second direction to a second position. The test fixture also includes a light source and a light sensor disposed so that when the element is in the second position, light from the light source passes through the void through the element having a void therethrough and is then detected by the light sensor. | 6 |
BACKGROUND OF THE INVENTION
This invention relates to a motorcycle mounted with a V shaped engine and more particularly to an improved exhaust arrangement for a motorcycle with an engine having a rearwardly directed exhaust port.
In many types of motorcycles, an engine is employed that has a rearwardly directed exhaust port. For example, motorcycles having V type engines with the crankshaft mounted transversely to the longitudinal direction of the motorcycle normally have at least the exhaust ports of the rear bank of cylinders extending in a rearward direction. It is a common practice in motorcycle construction to employ a rear wheel suspension in which the rear wheel is suspended for pivotal movement by means of a pair of trailing arms, one at each side of the motorcycle. The forward pivot point of the trailing arms is disposed closely adjacent the rear of the engine so as to maintain a relatively short wheel base for the motorcycle. In some applications, therefore, it is necessary to route the exhaust pipe from the rearwardly facing exhaust port downwardly through the area of the rear of the pivot axis of the trailing arms and forwardly of the rear wheel. In order to permit sufficient clearance for suspension travel, this exhaust pipe routing has necessitated a longer than desired wheel base for the motorcycle. In addition, when the motorcycle is serviced and the rear wheel and rear wheel suspension is removed, it has been necessary to remove the exhaust pipe with arrangements of this type. Alternatively, the pivot axis for the rear trailing arms may be moved rearwardly sufficiently so that the exhaust pipe may pass downwardly between the engine and the forwardmost portion of the pivot axis. Of course, this arrangement may unnecessarily lengthen the wheel base of the motorcycle.
It is, therefore, a principal object of this invention to provide an improved arrangement of the exhaust and rear suspension systems of a motorcycle having an engine with a rearwardly directed exhaust port.
It is another object of this invention to provide a motorcycle construction that permits a compact arrangement and yet which facilitates servicing.
SUMMARY OF THE INVENTION
This invention is adapted to be embodied in a motorcycle having a frame, an engine with at least one cylinder having a rearwardly facing exhaust port, a rear wheel, and a pair of spaced apart suspension arms suspending the rear wheel for pivotal movement relative to the frame. In accordance with the invention, the arms are pivotally supported by the frame by independent, spaced apart pivots with a gap therebetween. An exhaust pipe extends from the exhaust port through the gap between the independent pivots.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a side elevational view of a portion of a motorcycle constructed in accordance with this invention.
FIG. 2 is a perspective view of the portion of the motorcycle including the engine exhaust system and forward portion of the rear wheel support.
FIG. 3 is a top plan view of the motorcycle with portions shown in phantom.
FIG. 4 is a cross-sectional view taken along the line 4--4 of FIG. 3.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
A motorcycle constructed in accordance with this invention is illustrated partially and is identified generally by the reference numeral 11. In the drawings and specifically in FIG. 1, the front wheel, front wheel suspension and handlebar assembly has not been illustrated since this portion of the motorcycle forms no part of the invention.
The motorcycle 11 includes a frame assembly, indicated generally by the reference numeral 12 in which an engine, indicated generally by the reference numeral 13, is supported in a known manner. The engine 13 is of the V type and is disposed with its crankshaft extending transversely of the motorcycle 11. As a result, the engine 13 has a forwardly disposed bank of cylinders 14 and a rearwardly disposed bank of cylinders 15. In the preferred embodiment of the invention as illustrated, each bank of cylinders 14 and 15 includes two cylinders. Therefore, the engine is of the V four type. The engine is water-cooled and for that purpose a cooling radiator 16 is supported at the upper portion of the frame assembly 12.
Each cylinder of the front back 14 is provided with a respective intake pipe 17 which may include a carburetor and which extends generally vertically upwardly in the valley between the V of the engine. In a like manner, each of the cylinders of the rear bank 15 is also provided with a respective upwardly directed intake pipe 18 which may also include a carburetor. The intake pipes 17 and 18 extend upwardly into a recess formed in a saddle type fuel tank 19 that is supported in a known manner by the frame assembly 12. An intake device may be positioned in this recess and which communicates with an inlet 21 that also extends into the V between the cylinder banks 14 and 15.
The exhaust ports of the forward bank 14 extend forwardly and are served by respective exhaust pipes 22 that extend downwardly and outwardly toward the sides of the motorcycle beneath a combined crankcase and transmission 23 of the engine 13. The exhaust pipes 22 each terminate at respective inlets 24 formed at the outer sides of an exhaust expansion device 25 that extends transversely across the motorcycle 11 and beneath the rearward portion of the combined crankcase and transmission assembly 23. The device 25 may comprise purely an expansion chamber or, alternatively, may serve this function as well as some additional muffling function to that achieved by the expansion chamber.
The exhaust ports of the rear bank of cylinders 15 face rearwardly. Therefore, in order to route the exhaust pipes from these exhaust ports to the expansion chamber 25 for eventual discharge to the atmosphere, the exhaust pipes must be located so as to not interfere with the suspension system for the rear wheel, to be described, and also to provide for easy servicing. The rear suspension system is, therefore, designed to achieve this result in accordance with the invention.
A rear wheel 26 is rotatably supported at the rear end of a pair of trailing arms 27 and 28. The illustrated embodiment, the rear wheel 26 is shaft driven by means of a drive shaft 29 that passes through the hollow interior of the arm 27.
Conventionally, it has been the practice to join the arms 27 and 28 at their forward point and to provide a single transversely extending pivot for these arms. With such an arrangement, the exhaust pipes from the rear bank of cylinders 15 must pass either forwardly of the connecting pivot or rearwardly of it. If the exhaust pipes pass forwardly of the rear pivot for the arms 27 and 28, the wheel base may be increased excessively. If, on the other hand, the exhaust pipes pass rearwardly of this pivot, the wheel base is still lengthened because the exhaust pipes must clear the rear wheel 26 and allow for suspension travel. In addition, servicing is rendered difficult because it is necessary to remove these rear exhaust pipes before the rear wheel 26 and suspension arms 27 and 28 may be removed.
In accordance with this invention, an arrangement is provided wherein the exhaust pipes may be conveniently located without lengthening the wheel base and without interfering with the servicing of the motorcycle. To this end, the frame assembly 12 is provided with a pair of laterally spaced portions 31 and 32 that are disposed at opposite sides of the motorcycle. The portions 31 and 32 carry respective pivot pins 33 and 34 that journal the forwardmost portion of the arms 27 and 28, respectively. A universal joint (not shown) for the drive shaft 29 is disposed so that it lies at the pivot axis 33 so as to accommodate the suspension movement about this pivot axis. The arms 27 and 28 are interconnected at their forward ends by means of a gusset plate 35. The forward end of the gusset plate 35 is formed with a relief 36 and the pivot shafts 33 and 34 terminate at a spaced distance from each other in proximity to this relief by means of a gap, introduced generally by the reference numeral 37.
A pair of exhaust pipes 38 extend from each of the exhaust ports of the rear bank 15 downwardly through the gap 37 and in substantial alignment with the pivot axes defined by the pivot pins 33 and 34. The exhaust pipes 38 terminate in suitable inlets to the expansion chamber device 25. Because of the existence of the gap 37 and the passage of the exhaust pipes 38 through this gap, it should be readily apparent that the construction permits placement of the rear exhaust pipes without necessitating lengthening the wheel base of the motorcycle 11. In addition, the passage of the exhaust pipes 38 through the gap 37 permits the rear wheel 26 and suspension arms 27 and 28 to be removed from the motorcycle without necessitating removal of the exhaust pipes 38.
A pair of combined tailpipe and muffler assemblies 39 extend rearwardly from the exhaust expansion device 25 so as to discharge the exhaust gases from all of the exhaust pipes 22 and 38 to the atmosphere. These exhaust pipes and mufflers 39 extend on opposite sides of the rear wheel 26.
It should be readily apparent from the foregoing description that an extremely effective and yet compact exhaust and suspension arrangement is provided for a motorcycle having a V type engine. The arrangement permits compactness while at the same time avoiding difficulties in servicing. Although the invention has been described in conjunction with a V type engine, it should be understood that it may also be employed with an in-line engine or a single cylinder engine in which the exhaust port of the cylinders faces rearwardly although the invention has particularly utility in conjunction with V type engines which present significantly greater problems in connection with exhaust routing. Various other changes and modifications may be made without departing from the spirit and scope of the invention, as defined by the appended claims. | An exhaust and rear suspension system for a motorcycle that permits a compact, easily serviced arrangement. The engine is of the V type and has a bank of cylinders with rearwardly facing exhaust ports. The rear wheel is suspended by a pair of spaced apart trailing arms having independent forward pivot axes that define a gap therebetween through which exhaust pipes extend from the rearwardly facing exhaust ports. | 5 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to an electronic musical instrument which can be constituted at low cost using a system of the type in which frequency information corresponding to the note of a key is generated as a frequency number on a non-real time basis.
2. Description of the Prior Art
Heretofore, there has been employed in electronic musical instruments a system which is provided with means for generating as a frequency number, frequency information corresponding to a key and accumulates it on a real time basis, as proposed, for example, in U.S. Pat. No. 3,743,755. FIG. 1 is a block diagram showing the arrangement of such a prior art system. In FIG. 1, a frequency number (an F number) corresponding to key information derived from a key assignor 1 is read out from an F number memory 2 which is frequency number generating means, and a shift register 4 is shifted by a shift clock in synchronism with the timing at which the key information is provided. By an accumulator arranged to feed back the output from the shift register 4 to an adder 3, the F number is accumulated to obtain frequency information. In this case, the system arrangement is very simple but it has turned out that if the system is equipped with an actually required scale and functions, the cost of the shift register 4 would be unexpectedly high; hence, the conventional system is not always practical. The reason is as follows:
Consider the access time of the F number memory 2. Assuming, for example, that the sample frequency of the frequency information is 62.5 KHz, and that the key assignor 1 assigns 16 channels, for example, eight channels for an upper keyboard, seven channels for a lower keyboard and one channel for a pedal keyboard, the conventional shift register 4 is required to have 16 stages and the shift clock is of 16×62.5 KHz=1 MHz. Accordingly, it is desirable to execute an F number access from the F number memory 2 and the additive operation within a period of one μs.
Further, for obtaining sufficient frequency accuracy, 22 or more bits, for example, 24 bits are necessary. In the case of forming a gate circuit by individual parts as of TTL, its operating speed is not so important but its cost is high. When using, for example, a master slice system of a semi-custom LSI composed of CMOS's which is considered to be less costly, a period of about 500 nanoseconds is required for the abovesaid addition, so that the F number memory 2 must be formed by an element which is of short access time and consequently expensive.
In the case where the shift register 4 is a 24-bit, 16-stage shift register and is formed as an LSI, seven gates are needed for each stage of the shift register; namely, 24×16×7=2688 gates are required in all and even these gates alone cannot be accomodated in a general purpose master slice system. If these gates are provided externally, then 48 lines, that is, 24 connection lines between the adder 3 and the shift register 4 and 24 feedback lines from the shift register 4 are connected with pins of the master slice, but the existing master slice has only about 56 pins, and hence it is short of pins as a whole and cannot be employed. With a novel master slice, the use of the semi-custom LSI loses its meaning and the cost becomes rather high.
SUMMARY OF THE INVENTION
It is therefore an object of the present invention to provide an electronic musical instrument which employs the system of generating frequency information as a frequency number and is suitable for fabrication as a semi-custom LSI using inexpensive elements.
Another object of the present invention is to provide an electronic musical instrument which employs a complete master-slice arrangement between a buffer memory and a temporary memory and is stable in performance without using a large capacity shift register.
Briefly stated, the electronic musical instrument of the present invention is characterized by the provision of a frequency number memory for storing frequency numbers respectively corresponding to the notes of keys and sending out the frequency number corresponding to key information from a key assignor, means for executing an operation in units of the frequency number a plurality of times and transferring the result of each operation to a buffer memory, and a memory for storing the operation results.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a block diagram showing a prior art example;
FIG. 2 is a block diagram illustrating the arrangement of an embodiment of the present invention;
FIG. 3 is a detailed explanatory diagram of the embodiment shown in FIG. 2;
FIG. 4 is a timing chart explanatory of the operation of the embodiment depicted in FIG. 2; and
FIG. 5 is a connection diagram illustrating a specific example of one part of a control circuit employed in the embodiment of FIG. 2.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring first to FIG. 2, the present invention will be described in detail.
In the present invention, a frequency number (F number) is accumulated on a non-real time basis and the operation result is stored in a buffer memory by making use of a write slot of the buffer memory which is subject to time-division control in its read and write slots, while at the same time frequency information is read out from the buffer memory utilizing its read slot. In FIG. 2, when the F number corresponding to key information from the key assignor 1 is read out from the F number memory 2, it is stored in a register (#1)11. At the same time, the content of a temporary memory 12 which has stored therein the result of a previous accumulation is read out and stored in a register (#2)13, but, in a first readout of the F number memory 2, no content of the temporary memory 12 is read out. In a first accumulation, a selector 14 sends out the output from the register (#2)13 to an adder 15, wherein it is added with the content of the register (#1)11 and the added output is stored in a register (#4)16. Thereafter, the selector 14 sends out the output from the register (#4)16 to the adder 15, executing the accumulation under the control of a control circuit 19. The result of each accumulation is stored in a buffer memory 17 utilizing its write slot. After the accumulation is performed a preset number of times, the accumulation result is stored in a register (#3)18. The content of the register (#3)18 is stored in the temporary memory 12 at the same time as the next key information from the key assignor 1 is processed in the same procedure as mentioned above. The keys which each correspond to a note, are assumed to be part of the key assignor 1.
A detailed description will be given, with reference to FIG. 3, of the operation of this embodiment. In FIG. 3, when the input slot of the key information from the key assignor 1 is a channel 1, an F number corresponding to the key information of the channel 1 is provided from the F number memory 2 and stored in a first stage of the register (#1)11 by latch signals N H L (for latching the higher order of the F number) and N L L (for latching the lower order of the F number). In this embodiment, the F number is set to be 16-bit.
Since an ordinary 8-bit output type memory is used as the F number memory 2, the high-order eight bits of the F number are stored in the memory 2 at the position where the least significant bit of an address signal is 0 and the low-order eight bits are stored at the position where the least significant bit is 1. Accordingly, ROM N H /N L selecting signal is connected to at least significant bit address of the F number memory 2. Table 1 shows examples of F numbers which are stored corresponding to addresses thus given. For the key information from the key assignor 1, codes representing notes are caused to correspond to addresses other than the least significant bit addresses.
TABLE 1______________________________________Address F number stored______________________________________00000000 High-order eight bits of C.sub.200000001 Low-order eight bits of C.sub.200000010 High-order eight bits of C#.sub.200000011 Low-order eight bits of C#.sub.200000100 High-order eight bits of D.sub.200000101 Low-order eight bits of D.sub.2. .. .. .______________________________________
As shown in FIGS. 4(a) to (c), the operation for the channel 1 is performed following timing slots t 1 to t 32 in the period in which the key information input slot is a channel 2 but the operation is impossible with the F number alone. For each operation, the result of the previous operation is required. By address information from the control circuit 19, the operation result is read out from the temporary memory 12 by steps of four bits in read slots R 0 , R 1 , . . . R 5 . In this embodiment, an ordinary 4-bit output type memory is employed as the temporary memory 12.) and latched by latch signals R 0 L, R 1 L, . . . R 5 L and stored in the register (#2)13. The F number is read out in the subsequent read slots N H and N L and stored in a first stage of the register (#1)11. In this way, the F number and the previous operation result necessary for the operation for the channel 1 which is executed in the next channel 2 are prepared while the key information input slot is the channel 1. On the other hand, if the result of an operation for a channel 15 which is executed when the key information input slot is a channel 16 is not stored in the temporary memory 12, then an operation in the next channel 15 cannot be executed, so that the result of the last operation is latched by a t 1 latch signal and stored in the register (#3)18. By address information from the control circuit 19, this operation result is written, by steps of four bits, in the temporary memory 12 put in its write state by φ 6 , via gates which are turned ON by gate signals W 0 G, W 1 G, . . . W 5 G.
In this way, there is set up in the temporary memory 12 an area of at least six words for each of the channels 1 to 16 as shown in FIG. 4(c). When the key information input slot is the channel 2, the F number of the channel 2 is similarly read out from the F number memory 2 and, at the same time, the operation results of the channels 2 and 16 are respectively read out from the temporary memory 12 or stored therein. Of the F number corresponding to the channel 1 and the previous operation result which are necessary for the operation of the channel 1, the operation result loaded in the register (#2)13 is sent out to the selector 14 in preparation for the current operation. The F number loaded in the first stage of the register (#1)11 is shifted to a second stage by the t 1 latch signal which provides timing in the second stage becomes unnecessary for the operation.
Upon receiving a t 1 time slot pulse, the selector 14 provides the previous operation result to the adder 15 in a first time slot. Accordingly, the previous operation result and the F number are added together in the adder 15. The added output is latched and stored in the register (#4)16 by the rise of φ 1 representing the start of the time slot t 2 . Further, the added output is written in the buffer memory 17 by buffer memory address information from the control circuit 19 and φ 1 which puts the buffer memory 17 in its write state in the latter half of the time slot t 1 . After the time slot t 2 the selector 14 provides the output from the register (#4)16 to the adder 15, so that the F number is added for each of the time slots t 2 , t 3 , t 4 , . . . t 32 and the added result is derived at the output of the adder 15. The operation result is transferred to and loaded in the buffer memory 17 by φ 1 and the address information from the control circuit 19.
The operations described above are sequentially performed in the channels 1 to 16. The operation data which is transferred to the buffer memory 17 in this time is as large as 32 words×16=512 words.
φ 1 to φ 6 in FIG. 4(d) show the waveforms of frequency dividing clocks of 4 MHz and FIGS. 4(e) to (j) show the timing of generation of control signals which are supplied from the control circuit 19 to the respective components described above. FIG. 4(e) show the write gate signal W n G and the read latch signal R n L for the temporary memory 12, FIG. 4(f) the latch signals N H 1 and N L L for loading the F number in the register (#1)11, FIG. 4(g) the ROM N H/N L select signal and FIG. 4(b) the aforesaid operation slot t 1 latch signal and t 1 time slot pulse. FIG. 5 illustrates an example of the circuit arrangement of the control circuit 19 for generating control signals of predetermined timing which are applied to respective circuits. A fundamental clock of 4 MHz is applied to a frequency divider, wherein it is divided into frequencies φ 0 to φ 6 such as shown in FIG. 4(d), which are each divided into a normal output and an inverted output. These outputs are provided via a decoder 22 to gate groups 23 and 24, whereby it is possible to produce the write gate signal W n G and the read latch signal R n L depicted in FIG. 4(e). In a likewise manner, the other control signals shown in FIGS. 4(f) to (i) can be obtained through the use of required gates or flip-flops but no detailed description will be given.
With the above arrangement, the operation data 512 words of the channels 1 to 16 are transferred by the address information from the control circuit 19 to the buffer memory 17 to obtain frequency information but, in this case, it is necessary to prevent that the non-real time basis in the operation affects the frequency information. Table 2 shows an example of the arrangement of the buffer memory 17 for such a purpose.
TABLE 2______________________________________ Area A Area B .THorizBrace. .THorizBrace.______________________________________Address 1 . . . 32 33 . . . 64 . . . 481 . . . 512 SameSlots for opera- t.sub.1 . . . t.sub.32 t.sub.1 . . . t.sub.32 . . . t.sub.1 . . . t.sub.32 astion of loaded .BHorizBrace. .BHorizBrace. .BHorizBrace. leftdata 1CH 2CH 16CH______________________________________
Two 512-word memory areas A and B are provided, which are used for read and transfer alternately with each other. At first, the operation data are transferred to respective addresses of the area B in the order 1CH 1, 2, . . . 32, 2CH 33, 34, . . . 64 . . . 16CH 481, 482 . . . . In synchronism with this transfer data previously transferred to and stored in the area A are read out therefrom in the order 1CH, 2CH, . . . 16CH, that is, in the order of addresses 1, 33, . . . 481, 2, 34, . . . 482, . . . 32, 64, . . . 512. The data transfer to the area B is completed before completion of the readout of the area A. Next, the data thus stored in the area B is read out therefrom and data is transferred to the area A. The influence of the non-real time operation can be eliminated by operating the data as one group for each channel on the non-real time basis in the one area and by reading out the data from the other area on the time divided basis for each channel. Further, according to this method, when the clock input is set to 4 MHz, 32 μs×16 channels=512 μs corresponds to 32 sample points of each channel as seen from FIG. 4, so that the sample frequency of the essential frequency information is 62.5 KHz. This is the same as in the case of FIG. 1 but since the access time slots of the F number memory 2 and the temporary memory 12 can be set to 2 μs as depicted in FIGS. 4(e) to (g), there is no need of employing high-speed, expensive memory elements. This is very advantageous for the reduction of manufacturing costs and the stabilization of performance.
In the present invention, the registers (#1)11, (#2)13, (#3)18 and (#4)16, the selector 14 and the adder 15 shown in FIG. 3 can be constituted by the master slice system of the semi-custom LSI and the number of input/output lines required is 31, which can sufficiently be accomodated in the existing master slice. The smaller the number of input/output lines is, the lower the cost of the master slice becomes. The buffer memory and the temporary memory can also be formed by inexpensive memory elements of 4 bits ×1K word structure.
In the case where the prior art example of FIG. 1 accumulates the frequency number on a real time basis using a shift register, a first problem is that high-speed clocks are needed which calls for expensive memory elements and a second problem is that since a number of gates are required in the shift register, it is impossible to employ a master slice of a recent economical semi-custom LSI. In the present invention, a buffer memory and a temporary memory are provided in place of the shift register and there are provided between the buffer memory and the temporary memory an F number memory latch register, a temporary memory write/read register and an accumulator composed of a selector, an adder and a register. With such an arrangement, by providing two areas in the buffer memory and by alternating read and write of operation data between the two areas, the access time slots of the F number memory and the temporary memory can be extended twice as long as in the prior art, permitting the use of inexpensive memory elements; thus, the abovesaid first problem of the prior art can be settled. With respect to the second problem, the arrangement between the buffer memory and the temporary memory can completely be mastersliced, providing stable performance and low cost.
As has been described in the foregoing, according to the present invention, it is possible to obtain an electronic musical instrument which appears to be more complex than the prior art arrangement of FIG. 1 but is completely free from problems in practical use, inexpensive as a whole and stable in performance.
It will be apparent that many modifications and variations may be effected without departing from the scope of the novel concepts of this invention. | An electronic musical instrument which can be manufactured at low cost using a system of generating frequency information corresponding to the note of each key as a frequency number on a non-real time basis. The electronic musical instrument is provided with a frequency number memory for storing the frequency number corresponding to the note of each key and delivering the frequency number corresponding to key information from a key assignor, means for executing an operation in units of the delivered frequency number a plurality of times and transferring the operation result to a buffer memory upon each execution of the operation, and a memory for storing the results of the operation executed the plurality of times. | 6 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a continuation of and claims priority to U.S. patent application Ser. No. 11/026,442 filed on Dec. 30, 2004, now U.S. Pat. No. 7,279,197, which is a continuation of and claims poriority to U.S. application Ser. No. 10/267,943 filed Oct. 9, 2002, now U.S. Pat. No. 6,849,198, which claims priority under 35 U.S.C. §119(e) to U.S. Provisional Patent Application No. 60/327,877 filed on Oct. 9, 2001. Priority is claimed to each of these applications, and the subject matter of each of these applications is expressly incorporated herein.
BACKGROUND OF THE INVENTION
The use of freezing point depressants to remove hard-packed snow and ice from pavements has been a common practice by highway maintenance crews for decades. Each new freezing point depressant or chemical that is brought into the market has its own unique set of properties. Some of the depressants are thicker than others, while others are more concentrated. Others may have unpleasant odors, while others may work only at warm temperatures.
One of the first chemicals to be used by road maintenance crews was sodium chloride (NaCl), more commonly known as road salt. Initially, this chemical was applied as a solid, which rapidly went into solution in the presence of snow, ice or water. Typically, chemicals such as road salt have been applied during storms when temperatures were 20° F. or warmer in an attempt to melt snow as it fell and limit bonding to the pavement. Chemicals have also been applied after a storm to remove snow and ice that has bonded to the surface.
New methods of snow and ice removal are constantly being sought. More particularly, methods of snow and ice removal that do not adversely affect the environment and methods that decrease the volume of chemicals required are most sought.
SUMMARY OF THE INVENTION
In one aspect, the invention provides a method of inhibiting or preventing bonding between snow or ice and a substrate. The method includes applying an adhesive to the substrate, broadcasting an aggregate onto the adhesive to form an aggregate-adhesive, and applying an anti-icing chemical onto the aggregate-adhesive.
In another aspect, the invention provides an anti-icing composition. The composition includes an adhesive and an aggregate. At least a portion of the aggregate is encompassed by the adhesive and at least a portion of the aggregate is not encompassed by the adhesive and has a plurality of pores. The composition also includes an anti-icing chemical at least partially filling one of the pores.
In a further aspect, the invention provides another anti-icing composition. The composition includes an adhesive at least partially encompassing limestone having pores, and an anti-icing chemical at least partially filling at least one pore of the limestone.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a melted area of a road having an embodiment of the invention applied thereto.
FIG. 2 is a perspective view of a frost growth chamber.
FIG. 3 is a perspective view of a moisture generator.
FIG. 4 is perspective view of a frost growth on test samples.
FIG. 5 is a perspective view of a bond strength measurement device.
FIG. 6 is a diagram depicting load block and aggregate sample.
FIG. 7 is a perspective view of a sample mounted in a measurement device.
FIG. 8 is a graph depicting bond strength reduction for quarry tile aggregate (TS-A) with calcium magnesium acetate (CMA) applied thereto.
FIG. 9 is a graph depicting bond strength reduction for quarry tile aggregate (TS-A) with potassium acetate (KA) applied thereto.
FIG. 10 is a graph depicting bond strength reduction for quarry tile aggregate (TS-A) with propylene glycol (PGU) applied thereto.
FIG. 11 is a graph depicting bond strength reduction for quarry tile aggregate (TS-A) with sodium chloride (NaCl) applied thereto.
FIG. 12 is a graph depicting bond strength reduction for Levy Co. Slag aggregate (TS-B) with calcium magnesium acetate (CMA) applied thereto.
FIG. 13 is a graph depicting bond strength reduction for Levy Co. Slag aggregate (TS-B) aggregate with propylene glycol (PGU) applied thereto.
FIG. 14 is a graph depicting bond strength reduction for Levy Co. Slag aggregate (TS-B) aggregate with sodium chloride (NaCl) applied thereto.
FIG. 15 is a graph depicting bond strength reduction for London Co. limestone aggregate (TS-C) aggregate with calcium magnesium acetate (CMA) applied thereto.
FIG. 16 is a graph depicting bond strength reduction for London Co. limestone aggregate (TS-C) with potassium acetate (KA) applied thereto.
FIG. 17 is a graph depicting bond strength reduction for London Co. limestone aggregate (TS-C) with propylene glycol (PGU) applied thereto.
FIG. 18 is a graph depicting bond strength reduction for London Co. limestone aggregate (TS-C) with sodium chloride (NaCl) applied thereto.
FIG. 19 is a graph depicting bond strength reduction for Turunen, Inc. limestone aggregate (TS-D) with calcium magnesium acetate (CMA) applied thereto.
FIG. 20 is a graph depicting bond strength reduction for Turunen, Inc. limestone aggregate (TS-D) with potassium acetate (KA) applied thereto.
FIG. 21 is a graph depicting bond strength reduction for Turunen, Inc. limestone aggregate (TS-D) with propylene glycol (PGU) applied thereto.
FIG. 22 is a graph depicting bond strength reduction for Turunen, Inc. limestone aggregate (TS-D) with sodium chloride (NaCl) applied thereto.
FIG. 23 is a graph depicting bond strength reduction for Corps of Eng. limestone (TS-E) with calcium magnesium acetate (CMA) applied thereto.
FIG. 24 is a graph depicting bond strength reduction for Corps of Eng. limestone (TS-E) with potassium acetate (KA) applied thereto.
FIG. 25 is a graph depicting bond strength reduction for Corps of Eng. limestone (TS-E) with propylene glycol (PGU) applied thereto.
FIG. 26 is a graph depicting bond strength reduction for Corps of Eng. limestone (TS-E) with propylene glycol (PGU) applied thereto.
Before one embodiment of the invention is explained in detail, it is to be understood that the invention is not limited in its application to the details of construction and 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 or being carried out in various ways. Also, it is understood that the phraseology and terminology used herein is for the purpose of description and should not be regarded as limiting. The use of “including” and “comprising” and variations thereof herein is meant to encompass the items listed thereafter and equivalents thereof as well as additional items. The use of “consisting of” and variations thereof herein is meant to encompass only the items listed thereafter. The use of letters to identify elements of a method or process is simply for identification and is not meant to indicate that the elements should be performed in a particular order.
DETAILED DESCRIPTION OF THE INVENTION
Within the last ten years, environmental concerns have dictated the search for new chemicals as well as methods to decrease the amount of chemical used in snow and ice removal and prevention. One way to decrease the volume of chemicals is to limit the amount of hard-pack snow that needs to be removed from the surface after a storm. The invention includes a new method of pavement deicing that reduces bonding of snow and ice to the pavement. The refined concept is known as “anti-icing”.
In its simplest form, anti-icing comprises the application of chemicals prior to a predicted storm in an attempt to limit bonding to the pavement surface. In a low-precipitation-volume storm, the chemical has the potential to melt all frozen precipitation as it hits the surface. Generally speaking, the amount of chemicals required to inhibit and prevent bonding of snow and ice to the road is less than the amount required to melt snow and ice that has already bonded to the road. In heavier storms, the chemical keeps bonding to a minimum and allows for easy mechanical removal. In the event of predicted freezing rain events and frost events, chemicals that are applied prior to the storm have a marked effect on keeping the pavement from getting slippery due to ice.
In a preferred embodiment of the anti-icing methods, an adhesive is applied to pavement on a road, bridge, airport runway, tarmac or any other surface on which a vehicle may travel which may be covered by ice or snow. The adhesive acts to seal the pavement, thereby keeping water and salt from seeping through cracks or voids in the road. The adhesive also provides a slick, slippery overlay coating. Another goal of applying the adhesive is to repair delaminations, potholes and cracks. In addition, the surface may also be cleaned by shotblasting the pavement in order to remove any remaining contaminants, or by using oil-free compressed air to blow off and remove remaining dust and debris. The adhesive may be applied by using a notched squeegee at pre-specified rates. Additionally, the adhesive may be applied by using a brush or a sprayer. Any conventional adhesive application may be used. A wide variety of adhesives are suitable for use with the invention. The most preferred types of adhesives include epoxies, styrenes, methyl-methacrylate, as well as tar. One example of an epoxy follows, although this particular epoxy should in no way be construed as being limiting in terms of the types of epoxies that may be used. It is important, however, that the adhesive does not fill up or block the voids and pores of the aggregates discussed below so that no available space exists for the chemicals to fill. Typically, the thickness of the adhesive on the substrate is about ⅛″.
One preferred epoxy is PRO-POXY TYPE III D.O.T., which is a solvent-free, moisture insensitive, 100% solids, low modulus, two component bonding agent distributed by Unitex, Kansas City, Mo. PRO-POXY TYPE III D.O.T. meets ASTM-C-881 Type III, Grade 1, Classes B & C. The properties of this particular resin follow.
TABLE 1 ASTM C-881 LABORATORY TESTS RESULTS SPECIFICATIONS RESIN PROPERTIES Mix Ratio 1:1 by volume None D-695 Compressive Modulus 64,820 130,000 maximum D-638 Tensile Strength 2,610 psi None D-638 Tensile Elongation 49% 30% minimum C-882 Bond Strength (14 day 3,470 psi 1,500 psi minimum cure) D-570 Absorption 0.19% 1.0% maximum C-881 Gel Time 30 minutes 1 30 minutes maximum C-881 Brookfield Visc. RV3 1425 cps 2000 cps maximum @20 rpm D-2240 Shore D Hardness 69 None C-883 Shrinkage Pass None C-884 Thermal Compatibility Pass None AASHTO T-277 Chloride Ion 0.9 coulombs None Permeability Grout Properties Sand to Resin 3.5:1 by volume C-579 2 Compress. Strength 3 hrs 1100 psi N/A C-579 2 Compress. Strength 24 hrs 7500 psi N/A C-579 2 Compressive Strength 48 hrs moist cure 7500 psi N/A
Subsequently, in a preferred embodiment, aggregate is broadcast onto the adhesive. As used herein, the term “broadcast” is meant to refer to sprinkling, dropping, or spraying dry aggregate over the wet epoxy. The aggregate may be angular, grained silica sand, basalt having less than 0.2% moisture, flint, chipped limestone or dolomite, free dirt, clay, etc. The silica sand or basalt may have a minimum MOHS scale hardness of 7 unless otherwise approved. Typically, the aggregate is about ⅛ inch to ¼ inch, although aggregate sized from 1/16 inch to ½ inch may be used. The thickness of the aggregate or the substrate is generally about ¼ inch to ¾ inch. Once the aggregate is glued to the surface using the adhesive, the aggregate may be ground. For example, the aggregate may be ground to about ¼ inch to about ⅜ inch. More particularly, once the adhesive has set, a surface grinder may be employed to cut off portions of the jagged surface. The resultant surface looks a lot like a light colored pavement, although it is rougher. This process makes the surface very much like a solid limestone or dolomite slab with enough texture to keep good surface friction.
Overall, the most preferred type of aggregate, however, is limestone or dolomite. The type of limestone or dolomite used in conjunction with the invention may be dictated by regional availability. Some examples of limestone and dolomite include three aggregates chosen from the approved source list at the Michigan Department of Transportation (MDOT). For example, MDOT Pit #92-11 (dolomitic limestone), London Aggregates Co. and MDOT Pit #58-10 (air cooled blast furnace slag), E.C. Levy Co. can all be used in conjunction with the invention. Each of these limestones exhibits a high absorptivity. Other examples include limestones originating from a quarry operated by Turunen, Inc. in Pelkie, Mich., and another of unknown origin obtained from a Corps of Engineers armor stone pile on the Hancock Canal in Hancock, Mich.
After initially curing the first application of aggregate on the adhesive, excess aggregate may be removed from the surface. Shortly thereafter, a second course of adhesive and aggregate may be applied to the portion of the road or bridge, and excess aggregate may again be removed and the second course allowed to cure. Typically, each adhesive layer is about ¼ inch thick, although it may be as thin as ⅛ inch and as thick as ¾ inch. The second application of adhesive and aggregate is not required. At least a portion of the aggregate is generally encompassed by the adhesive in order for the aggregate to be secured to the surface or substrate. At least a portion of the aggregate may not be encompassed, i.e. it is exposed to ambient conditions, so that pores in the aggregate may be at least partially filled with an anti-icing chemical.
Once the aggregate and adhesive have cured, an anti-icing chemical, or a combination of anti-icing chemicals, is applied to the aggregate-adhesive. Generally, the application is accomplished by spraying the chemicals onto the aggregate-adhesive, although brush application as well as other known application techniques may be used. In other words, any method that enables chemicals to be applied to stretches of road or bridges is acceptable. Preferably, the anti-icing chemicals are applied in liquid form, although solid, powder and gaseous chemicals may be used. Any anti-icing chemical that acts as a freezing point depressant or lowers the freezing point of the ice and snow may be used with the invention. Preferred anti-icing chemicals include calcium magnesium acetate, potassium acetate, sodium acetate, sodium chloride, sodium formate, magnesium chloride, propylene glycol with urea additive, ethylene glycol with urea additive and potassium carbonate.
Some of the freezing point depressants tend to display a residual effect when used in conjunction with the aggregates described above. In other words, residual effect may be exhibited through a storm as the chemicals prevent bonding between the snow/ice and the pavement, and subsequently functions in a similar manner during the next storm. Residual effect is a characteristic of a chemical that allows it to function for an extended period of time during a single storm event, while also maintaining the potential to remain on the pavement in order to function in the event of subsequent storms.
In simple terms, residual effect means the invention is able to function again and again without the need for chemical reapplication. Certain combinations of chemicals and aggregates have the potential to greatly increase residual effect at the pavement surface. Some chemicals exhibit a better tendency for residual effect than others. FIG. 1 shows residual effect of a chemical on a pavement test section. In some cases, chemicals may be resistant to washing by storm and melt water, as well as the mixing action of traffic tires. This can contribute to increased residual effect.
When limestone is utilized as an aggregate, it tends to create a sponge-like pavement to which the anti-icing chemicals can be applied. Although the invention should in no way be limited by theory, it is believed, in part, that the limestone's porosity and ability to absorb imparts a residual effect. In any event, the combination of a limestone aggregate and an anti-icing chemical seems to greatly enhance the residual effect. In other words, some property of the limestone allows the anti-icing chemical to be absorbed into the limestone, but not too far from the surface of the limestone. As a result, new chemicals do not need to be applied to the limestone after every storm or event. Instead, the limestone aggregate and anti-icing chemical combination remains effective from storm after storm. It has also been found that by cleaning the surface of the aggregate/adhesive/chemical on the pavement, e.g. by a strong, intense water stream, the residual effect is further enhanced. In other words, this cleaning seems to “recharge” the surface after the surface has been exposed to a storm. The residual effect provides a semi-permanent anti-icing method that makes it unnecessary to reapply the anti-icing chemicals after each storm. Instead the chemicals can be sprayed, e.g. in October, before the winter season, and need not to be reapplied until after the storm season or later.
The chemicals tend to stay on or close to the area on which they are intended to be applied. As a result, these chemicals are less detrimental (if at all) to the environment. In addition, these chemicals are not wasted on the shoulder or ditch, which is often the case when pellets of sodium chloride are dropped on the road. In the case of bridges over fragile streams, chemical runoff into fragile streams is almost non-existent. The sponge-like action of the overlay holds the chemical in place and prevents it from being blown off by passing vehicle traffic, aircraft jet blast or propeller wash.
The overlay is rough in its applied state and eliminates the need to consider whether the surface is wet, because the particle roughness alleviates wetness. The overlay also eliminates stalled or backed-up traffic leading into airports, which is caused by airports having seemingly wet pavement surfaces. In addition, the anti-icing overlay system is rougher and has a higher overall friction value than either Portland cement or asphalt cement pavements. This roughness makes the traction, steering, and braking of rubber tires safer. It also prevents water or chemicals from infiltrating the pavement, reaching reinforcing steel and causing corrosive damage. This will prolong the life of concrete pavement, i.e. bridges, roads and runways.
A single application of liquid chemical can remain effective on the overlay for extended periods of time (e.g. as long as months) in the case of frost and freezing rain events. The overlay is applied on the surface of the existing pavement and will last five or more years before needing to be touched up. Chemicals can be re-applied whenever they are needed. Overall, by reducing the bond and bond strength between the snow and ice and the substance upon which automobiles and other vehicles travel, the chance of accidents occurring is reduced.
EXAMPLES
Example 1
Frost Growth and Ice Bond Mitigation
“Frost growth” and “ice bond mitigation” were performed to test anti-icing and residual effect. The test procedures for these follow.
In preparation for both the frost and bonding tests, aggregate samples were cut using water lubricated saws to avoid introducing any oils or other chemicals contacting the samples. A large cutoff saw was used for initial cutting and a smaller tile saw for the finish cuts.
A method was also devised to simulate the effect of water and tire action at the surface of a pavement, thereby determining how well a combination reacted to a storm event, and the potential for it to keep working through future storms. After the load simulation was completed the aggregates were left to thaw at room temperature. Once all ice was melted from the surface of the aggregates, a saturated sponge was used to wipe them clean. The sponge was passed over the aggregate surface five times. This procedure was meant to simulate the washing of the road surface by traffic and one storm event. After this process was completed the aggregates were left to air dry at room temperature until no visible signs of moisture remained on the blocks.
Frost Growth
To determine how well a chemical/aggregate combination could mitigate the formation of frost on the pavement surface, the phenomena that causes frost to grow was simulated. Frost forms on the pavement when a relatively warm, wet, air mass passes over a cold pavement section. The air mass must be adequately warm in order to contain water vapor that is unfrozen. The pavement must be cold enough to contribute to condensation and freezing of this liquid vapor. The two most common cold pavement scenarios are bridge decks cooled from beneath by the air and pavements where the base material is much colder than the air, which allows it to remain cold even if the air above it is warmer.
A frost growth chamber or control box was designed and built inside the KRC (Keweenaw Research Center) cold laboratory to simulate the frost growth phenomena and is shown in FIG. 2 . This box is approximately 4 feet long by 2 feet wide by 2 feet high. The inside of the box is insulated except on the bottom, which comprises a ½ inch thick aluminum plate. A light bulb and dimmer switch setup are used to heat the inside of the box to create a temperature gradient between the outside and inside of the box. With this setup, the coldroom can be set at 20° F., and the inside of the box can be kept at, for instance, 34° F. The insulated walls of the box work well to keep the inside air temperature constant while at the same time the high thermal conductivity of the aluminum plate on the bottom keeps that surface at a temperature much lower than the inside air. With this sort of temperature difference from the outside to the inside of the test box, thin pavement (or aggregate) samples can be placed on the aluminum inside the box, and their surface temperatures cooled well below the air temperature. The box is also equipped with a glass viewing door and internal thermocouples for various temperature measurements.
Once the method for simulating “warm” air on top of cold pavement was completed, a moist air on top of the samples was induced. Since it is known that the most severe frost growth occurrences are when a moist warm air mass flows very slowly (nearly calm conditions) over a cold substrate, this was the starting point for this part of the setup. Several different methods to produce frost within the test box were tested. The final setup was a network of 2 inch PVC pipe that is plumbed into the coldroom through the wall from the outside office. FIG. 3 shows the moisture generator or air system. A pipe is inserted through the wall and into one end of the frost box and a second pipe exits the other end of the box and back through the coldroom wall. FIG. 2 shows these pipes. Outside of the coldroom (in the office) is a large insulated cooler into which one of the PVC pipes is plumbed. A variable output fan mounted inside this box can be used to force air through the pipe. Exhaust air moves back through the other pipe into the office. Also located inside this box is a heated water reservoir that can be used to increase the amount of moisture flowing through the system.
A frost growth test was performed by setting the coldroom temperature to a desired value and also setting the temperature in the frost box to allow freezing from the bottom of a sample. Test samples are placed into the box and left there in an adjusted moisture regime. After a period of time, the samples are evaluated visually for frost growth. In general, the frost is quite obvious if it has formed to any degree. Attempts were made to quantify the existence of frost, but since the frost is highly fragile, it is not possible to measure it. FIG. 4 shows two tile samples inside the box. Each tile has chemical applied over one-half of the surface. In this case, the chemical is on the sides in the background. Each tile is frost covered in the foreground half (no chemical) and frost free in the background (chemical applied).
Bond Growth
FIG. 5 shows a bond strength measurement device. The assessment of bond strength reduction at the pavement interface was studied using a shear test in the cold lab. A device comprising a horizontal load cylinder with a load cell and distance/speed measurement sensors was set up in the KRC lab. This device was connected to a computer data acquisition system that collects and stores load and displacement throughout a test. The load cell used for these tests has a maximum range of 400 pounds and measures to a precision of approximately ±0.2 pounds. The distance measurement device measures to approximately ±0.0075 inches. Tests were performed at a speed of 0.0015 inches per second. A sample is mounted into this device and the resultant bond strength can be measured.
Ice was used instead of snow particles, since the two are essentially the same at high density. In order to get repeatable results in the lab many different scenarios were tried with the final sample setup as follows.
For example, aggregate samples of approximately ½ inches in thickness and 2 inches by 2 inches in plan were prepared. Wooden load blocks that are slightly larger than the stone coupons were set up with a small dam around the perimeter on one face. These dams are about ⅛ inches in height. The blocks can be set on a level surface, and the dam can be filled with water and frozen. This results in a ⅛ inch thick layer of ice on one face of the wooden block.
FIG. 6 shows a drawing of a load block system and FIG. 7 shows a sample mounted for testing. The water and block are left in the coldroom for two hours, at 25° F., or until the water has completely frozen. Once ice has fully formed, water is boiled in a separate container and an aluminum plate is placed in the boiled water. The water, aluminum plate, and aggregate samples are then brought into the coldroom with the ice samples. The hot aluminum plate is placed on the ice block for approximately fifteen seconds, or until a layer of water has formed. Once this has happened, the aggregates, which are still approximately room temperature (70° F.), are then placed on the water/ice sample. (Placing the block on the sample when its temperature is warmer than freezing aids in the bonding of the ice and aggregate.) The new combination is then left in the coldroom for approximately 30-45 minutes, or until the water has completely frozen. Once the water has completely frozen a hot soldering iron is used to melt away any excess ice that has formed around the aggregate beyond the surface plane. The sample is then mounted in a load simulator, which is connected to a data-logger. The load block and aggregate sample are locked into the device to assure a level pull. A load is applied to the sample at a rate of approximately 250 pounds per second, and is recorded by the data-logger by means of a load cell. The test data is then downloaded from the data-logger into a spreadsheet where the numbers can be manipulated to give a readable output. For these tests, the normal load is zero.
Results
Three aggregates were used from the approved sources list at the Michigan Department of Transportation (MDOT). Two samples were obtained from MDOT Pit #92-11 (dolomitic limestone), London Aggregates Co. and MDOT Pit #58-10 (air cooled blast furnace slag), E.C. Levy Co. Each of these exhibits a high absorptivity. Two other samples were obtained by KRC. Both of these are limestones, one of which comes from a quarry operated by Turunen, Inc. in Pelkie, Mich., and the other of which has an unknown origin and was obtained from a Corps of Engineers armor stone pile on the Hancock Canal in Hancock, Mich.
A fifth sample type was used as a very low absorptivity specimen. This is a natural quarry tile obtained from a local flooring dealer. These tiles are used for other chemical testing at KRC. They are slightly rough and very homogenous. They were chosen after years of testing to simulate the micro surface roughness of concrete pavement surfaces.
Absorptivities were measured for all of these five test samples and are contained in Table 2. The value is given as a percent of total weight of aggregate and was determined using a 24 hour soak period. This table also contains the test names given to each sample for use during the rest of this report.
TABLE 2
Aggregate Descriptions
Test
Aggregate source
Name
Absorptivity % (24 hr)
Quarry Tile
TS-A
0.27
Levy Co.
TS-B
5.49
London Agg.
TS-C
4.42
Turunen, Inc.
TS-D
1.73
Corps of Eng.
TS-E
1.22
Chemicals
Four chemicals were chosen for use in these tests. Liquids were chosen for this particular test, although other physical states of the chemicals may be utilized in conjunction with the invention. Liquid chemicals can be applied most uniformly to the surface of the aggregate samples. The four chemicals chosen for use in this example were liquid calcium magnesium acetate (CMA), potassium acetate (KA), propylene glycol with a urea additive (PGU), and liquid sodium chloride (NaCl).
Frost Mitigation
To determine how well a combination of aggregate and chemical reacts to the formation of frost, a number of tests were performed in the frost chamber. Aggregate coupons were placed into the chamber after being saturated with chemical in order to determine if frost would grow. For all tests, untreated coupons were also placed into the box to assure that frost was growing in the unit. After the set of tests were completed with saturated surfaces, the samples were washed and the samples were re-tested.
The first set of tests was conducted with the five test samples and four chemicals. Aggregate coupons were soaked in chemical for 24 hours to ensure a thorough covering of deicer. The samples were then removed and allowed to air dry. After this drying period, the soaked samples were placed in the frost chamber at 20° F. and left for 21 hours. Untreated coupons of the five stones were also placed in the chamber for comparison. The results are given in Table 3.
The first five entries in the table are the aggregate coupons that have had no chemical applied. Frost has grown on these samples as expected. The next 14 entries are for combinations of chemical and aggregate. The TS-B sample used with KA broke during testing and resulted in no values for this combination. None of the samples with chemical showed any frost growth. The D and E samples showed some wetness on the surface. This particular set of tests did not include NaCl.
Table 4 contains a similar set of results. In this test, the samples from the test in Table 3 were cleaned with the saturated sponge 25 times and the test was repeated. For this test, the results are the same as the previous set, with the exception of the TS-A samples. The washings removed enough chemical from these low absorptivity coupons and freezing has occurred. The D and E samples were again covered by small beads of water. These samples have absorptivities that are low enough that precipitated moisture does not soak in as it does on the B and C samples.
Table 5 is a test after 50 sponges (25 added to the previous test). All of the scenarios remain the same with the exception of the TS-B samples. The TS-B samples were washed to the point where freezing has occurred.
Table 6 contains the final set of data after another 25 sponge cleanings totaling 75. The results show a similar trend to the previous three tests.
TABLE 3
Frost Results - No Sponge Cleanings
Number of
Time in
Frost Chamber
Sample
Sponges
Frost Box (hr)
Temp ° F.
Results
TS-D Base
0
21
20
Layer of frost over entire sample
surface.
TS-E Base
0
21
20
Layer of frost over entire sample
surface.
TS-C Base
0
21
20
Layer of frost over entire sample
surface.
TS-B Base
0
21
20
Layer of frost over entire sample
surface.
IS-A Base
0
21
20
Layer of frost over entire sample
surface.
TS-D/PGU
0
21
20
No frost. Water beads on sample.
TS-D/LA
0
21
20
No frost. Water beads on sample.
TS-D/CMA
0
21
20
No frost. Water beads on sample.
TS-E/PGU
0
21
20
No frost. Water beads on sample.
TS-E/KA
0
21
20
No frost. Water beads on sample.
TS-E/CMA
0
21
20
No frost. Water beads on sample.
TS-C/PGU
0
21
20
No frost.
TS-C/KA
0
21
20
No frost.
TS-C/CMA
0
21
20
No frost.
TS-B/PGU
0
21
20
No frost.
TS-B/CMA
0
21
20
No frost.
TS-A/PGU
0
21
20
No frost.
TS-A/KA
0
21
20
No frost.
TS-A/CMA
0
21
20
No frost.
TABLE 4
Frost Results - 25 Sponge Cleanings
Number of
Time in
Frost Chamber
Sample
Sponges
Frost Box (hr)
Temp ° F.
Results
TS-D Base
25
28.5
20
Layer of frost over entire sample
surface.
TS-E Base
25
28.5
20
Layer of frost over entire sample
surface.
TS-C Base
25
28.5
20
Layer of frost over entire sample
surface.
TS-B Base
25
28.5
20
Layer of frost over entire sample
surface.
TS-A Base
25
28.5
20
Layer of frost over entire sample
surface.
TS-D/PGU
25
28.5
20
No frost. Water beads on sample.
TS-D/KA
25
28.5
20
No frost. Water beads on sample.
TS-D/CMA
25
28.5
20
No frost. Water beads on sample.
TS-E/PGU
25
28.5
20
No frost. Water beads on sample.
TS-E/KA
25
28.5
20
No frost. Water beads on sample.
TS-E/CMA
25
28.5
20
No frost. Water beads on sample.
TS-C/PGU
25
28.5
20
No frost.
TS-C/KA
25
28.5
20
No frost.
TS-C/CMA
25
28.5
20
No frost.
TS-B/PGU
25
28.5
20
No frost.
TS-B/CMA
25
28.5
20
No frost.
TS-A/PGU
25
28.5
20
Ice layer covering sample.
TS-A/KA
25
28.5
20
Ice layer covering sample.
TS-A/CMA
25
28.5
20
Ice layer covering sample.
TABLE 5
Frost Results - 50 Sponge Cleanings
Number of
Time in
Frost Chamber
Sample
Sponges
Frost Box (hr)
Temp ° F.
Results
TS-D Base
50
30
20
Layer of frost over entire sample
surface.
TS-E Base
50
30
20
Layer of frost over entire sample
surface.
TS-C Base
50
30
20
Layer of frost over entire sample
surface.
TS-B Base
50
30
20
Layer of frost over entire sample
surface.
TS-A Base
50
30
20
Layer of frost over entire sample
surface.
TS-D/PGU
50
30
20
No frost. Water beads on sample.
TS-D/KA
50
30
20
No frost. Water beads on sample.
TS-D/CMA
50
30
20
No frost. Water beads on sample.
TS-E/PGU
50
30
20
No frost. Water beads on sample.
TS-E/KA
50
30
20
No frost. Water beads on sample.
TS-E/CMA
50
30
20
No frost. Water beads on sample.
TS-C/PGU
50
30
20
No frost.
TS-C/KA
50
30
20
No frost.
TS-C/CMA
50
30
20
No frost.
TS-B/PGU
50
30
20
Ice layer covering sample.
TS-B/CMA
50
30
20
Ice layer covering sample.
TS-A/PGU
50
30
20
Ice layer covering sample.
TS-A/KA
50
30
20
Ice layer covering sample.
TS-A/CMA
50
30
20
Ice layer covering sample.
TABLE 6
Frost Results - 75 Sponge Cleanings
Number of
Time in
Frost Chamber
Sample
Sponges
Frost Box (hr)
Temp ° F.
Results
TS-D Base
75
72
20
Layer of frost over entire sample
surface.
TS-E Base
75
72
20
Layer of frost over entire sample
surface.
TS-C Base
75
72
20
Layer of frost over entire sample
surface.
TS-B Base
75
72
20
Layer of frost over entire sample
surface.
TS-A Base
75
72
20
Layer of frost over entire sample
surface.
TS-D/PGU
75
72
20
No frost. Water beads on sample.
TS-D/KA
75
72
20
No frost. Water beads on sample.
TS-D/CMA
75
72
20
No frost. Water beads on sample.
TS-E/PGU
75
72
20
No frost. Water beads on sample.
TS-E/KA
75
72
20
No frost. Water beads on sample.
TS-E/CMA
75
72
20
No frost. Water beads on sample.
TS-C/PGU
75
72
20
No frost. Moist surface.
TS-C/KA
75
72
20
No frost. Moist surface.
TS-C/CMA
75
72
20
No frost. Moist surface.
TS-B/PGU
75
72
20
Layer of frost over entire sample
surface.
TS-B/CMA
75
72
20
Layer of frost over entire sample
surface.
TS-A/PGU
75
72
20
Ice layer covering sample.
TS-A/KA
75
72
20
Ice layer covering sample.
TS-A/CMA
75
72
20
Ice layer covering sample.
A second set of frost growth tests was performed using the same aggregates as above with NaCl as the deicer. Coupons of each of the five test aggregates were coated with NaCl and placed in the frost box at 20° F. After 24 hours, frost had formed on all of the samples with the exception of some spots on the TS-E limestone. This test coupon has a small vein of darker and visibly different material through part of its interior. This vein did not grow frost. This indicates that a difference in stone may still show a no frost result even with NaCl. The frost on the coupons was more soft and loose compared to frost on untreated coupons. This indicates that there is still melt potential, but not enough to totally prevent frost growth.
A second test was devised using the coated coupons. The coupons were dried a second time but not washed. The dried samples were placed in the frost box at 25° F. and after 24 hours were all moist with no frost formed. The temperature was then dropped to 23° F. and the samples left for 24 hours. At this point, light frost formed on all of the test coupons. This frost was again quite loose and bordered on “slushy.” The veins on the TS-E sample again showed no frost growth.
Bond Strength Reduction
The graphs of FIGS. 8-25 are the results for the representative tests of the five final aggregates and four liquid chemicals. Each graph is depicted with a code such as TS-A/CMA ( FIG. 8 ). This is aggregate type TS-A with CMA applied. The graphs also each contain a line that is the “Baseline.” This is the average of a set of five tests performed on the coupon with no chemical applied. The solid black line shows the linear regression of the data, while the equation for this line is also given.
Turning specifically to FIG. 8 , which is indicative of the other Figures, the purple line with data points plotted as boxes is the baseline. This is the average bond strength of ice to this particular sample with no chemical applied. The blue line and diamond shaped data points are the load values for each test pull after the surface is washed. For instance, the first blue diamond is the de-bonding load after one washing (five sponge passes). The black line is the linear regression of the data. This line is plotted to show the trend of the return to baseline. The CMA, KA, and PGU were all tested at an interval of one washing (five sponges) between each shear test. The NaCl tests were performed at a more rapid pace due to time constraints caused by adding this chemical late in the test scope. The NaCl was tested at no washings, one washing and then at three, five and every two washings after that. This was accomplished by simply doubling the washes between tests.
FIGS. 8-11 show the data for the TS-A samples and the four chemicals. All four of these samples show a rapid return to baseline with a limited number of washings. In general, they have all gone back to a “no chemical” state with 15 washings or less.
FIGS. 12-14 show the results for the TS-B samples. As mentioned previously, the coupon used for KA broke during testing. Tests were performed on this coupon at zero, one and two washes. The results were 18, 41, and 65 pounds, respectively. No graph is included for this test. The baseline was 145. The coupon used for NaCl also broke after 10 washings ( FIG. 14 ). The three figures for this aggregate show a rapid return to baseline in all cases. The KA test was also nearly half way back to baseline after two washings. The broken coupons were not re-tested due to time and material constraints.
FIGS. 15-18 show the TS-C sample test data. These four tests show a better residual effect than the A & B samples.
The results for the TS-D samples are given in FIGS. 19-22 . All four of these combinations still function properly after 17 washings. The TS-E results are shown in FIGS. 23-25 .
This testing clearly shows that certain combinations of aggregate and deicing chemical can drastically reduce the formation of frost on pavements, as well as minimize the bond potential between ice and the pavement.
Frost growth tests show that in some cases, the occurrence of frozen water vapor precipitation (hoar frost or rime ice deposit) is nearly eliminated. Some limestones in combination with freezing point depressants show no freezing even after numerous washings. As a result, these applications can be used on bridge decks that are highly susceptible to frost, thereby keeping the deck ice free through numerous storm events. In contrast, testing on low absorptive samples show rapid re-freezing after only a few washings.
The same potential holds true for the reduction of bond strength with a single chemical application. In general, the same scenarios work well for residual effect for bond reduction as do for frost mitigation. In both cases, the limestones with medium absorptivities perform well with all chemicals tested under this scope. FIGS. 10 and 19 are good examples of the contrast between combinations. In FIG. 10 the residual effect is nearly gone after four washings. On the other hand, the combination in FIG. 19 is still working very well after 17 washings.
For both the frost and bond reduction testing, the tile samples were chosen to simulate a non-absorptive pavement, e.g., a pavement or bridge deck consistently covered with frost and icing for nearly every frost or freezing event even after chemicals were applied on the previous event. Any chemical that was applied has been washed off and there is little or no residual effect left. Considering the results for the tile samples, this is a good assumption. First, frost grows on these samples after the first set of washings. For the bond reduction the bond strength rises to a level comparable to the “no chemical” state after only a few washings. This is shown graphically by the trend given by the linear regression of the data. These regression lines show how rapidly a combination returns to the “no chemical” state after application of chemical. A steep line depicts a poor tendency for residual effect with a flat slope showing good chemical retention.
FIGS. 23 and 25 show combinations resulting in excellent residual reduction in bond strength. These are the TS-E limestones with CMA and NaCl. Both of these show bond strengths well below the baseline values even after 16 washings. This means that the pavement simulated by the tile samples could be coated with one of these aggregate/chemical combinations and the residual bonding could be drastically reduced. The CMA can eliminate frost down to 20° F. on this aggregate while the NaCl may eliminate frost down to about 23° F. In any case, both of these, and several other combinations tested show that a much safer pavement can be obtained by coating pavements that exhibit “poor” residual effect with “anti-icing” smart aggregate/chemical combinations.
Example 2
In another example, an 8 foot by 200 foot test section of anti-icing composition was applied to the edge of the tarmac at the FAA Technical Center in Atlantic City. For this example, Pro-Poxy Type III DOT epoxy obtained from Unitex, in Kansas City, Mo., was used as adhesive and applied to the tarmac substrate. More particularly, the adhesive was poured onto the tarmac, and then spread and thinned. The thickness of the adhesive on the tarmac was about ⅛ inch. Approximately 7500 pounds of crushed limestone aggregate obtained from Michigan Limestone Operations, Inc. was then broadcast onto the adhesive by sprinkling the aggregate out of a bucket. The thickness of the aggregate was about ½ inch, until it was ground to about ¼ inch to about ⅜ inch. The anti-icing chemical used in conjunction with this example will be chosen at a later date by FAA. About 5 gallons of this anti-icing composition will be sprayed using a chemical or tank sprayer onto the overlay prior to winter weather. The anti-icing chemical may or may not re reapplied. The FAA will be performing friction tests and icing tests on this section during the upcoming winter to complete the in field proof of concept.
Example 3
Also, connected to this test are two wear tests designed to determine how durable and resistant to wear these coatings are when installed on a pavement. MDOT personnel will perform one of these tests at the Michigan Department of Transportation (MDOT) pavement lab in Lansing, Mich. This is the standard test for aggregate wear and polishing for the State of Michigan. The other wear test will include a field test section near KRC that will monitor traffic and plowing on an actual road surface. These two tests should demonstrate are designed to prove that that overlays are durable and will not wear out rapidly.
Example 4
Another anti-icing composition is likely to be laid in the near future on a bridge deck for the Wisconsin Department of Transportation. The anti-icing composition would coat a twenty-four foot by one hundred and eighty foot bridge deck. The composition will likely be the same as the one applied in Example 2. The epoxy will be Pro-Poxy Type III DOT epoxy obtained from Unitex and the aggregate will likely be obtained form Northeast Asphalt in Shawano, Wis., and will be similar to that used in Example 2. | A method of inhibiting or preventing bonding between snow or ice and a substrate. The method includes applying an adhesive to the substrate, broadcasting an aggregate onto the adhesive, the aggregate having the capacity to receive an anti-icing chemical into the aggregate, and applying the anti-icing chemical onto the aggregate so that at least a portion of the anti-icing chemical is received into at least a portion of the aggregate. | 4 |
FIELD OF THE INVENTION
This invention is in the field of ester containing quaternary ammonium salts having utility as charge control agents for toners that also serve as adhesion promoters between toner and receiver sheets and as toner fusing temperature reducers.
BACKGROUND OF THE INVENTION
In the art of making and using toner powders, charge control agents are commonly employed to adjust and regulate the triboelectric charging capacity and/or the electrical conductivity characteristics thereof. Many different charge control agents are known which have been incorporated into various binder polymers known for use in toner powders. However, the need for new and improved toner powders that will perform in new and improved copying equipment has resulted in continuing research and development efforts to discover new and improved charge control agents.
Of potential interest are substances which not only serve as toner powder charge control agents, but also function as agents that provide additional results or effects. Such multi-functionality not only offers the potential for achieving cost savings in the manufacture and use of toner powders but also offers the potential for achieving toner powders with performance capabilities not heretofore known.
Charge control agents that contain either incorporated ester groups or incorporated quaternary ammonium salt groups are known ("Research Disclosure No. 21030" Volume 250, October, 1981, published by Industrial Opportunities, Ltd., Homerville, Havant, Hampshire, P091EF, United Kingdom) but charge control agents that contain both ester groups and quaternary ammonium groups in the same molecule are unknown, so far as now known.
SUMMARY OF THE INVENTION
This invention is directed to toner powders comprising a polymeric matrix phase which has dispersed therein at least one quaternary ammonium salt having incorporated therein at least one ester containing moiety that is bonded through an alkylene linking group to a quaternary ammonium nitrogen atom.
When incorporated into toner powders, such quaternary ammonium salts not only function as charge control agents, but also as toner powder fusing temperature depressants and paper adhesion promoters. These salts are preferably dispersed in the polymeric binder matrix phase comprising the core or body portion of a toner particle. These salts appear to have greater compatibility with polyester resins than prior art charge control agents that contain only an ester group or a quaternary ammonium group.
Toner powders containing these salts incorporated into the polymeric binder thereof can be used for producing developed toned images on a latently imaged photoconductor element, for transfer of the toned image from the photoconductor element to a receiver sheet, and for heat fusion of the toned image on the receiver, while employing processes and processing conditions heretofore generally known to the art of electrophotography.
Various other advantages, aims, features, purposes, embodiments and the like associated with the present invention will be apparent to those skilled in the art from the present specification taken with the accompanying claims.
DETAILED DESCRIPTION
(A) Definitions
The term "particle size" as used herein, or the term "size", or "sized" as employed herein in reference to the term "particles", means volume weighted diameter as measured by conventional diameter measuring devices, such as a Coulter Multisizer, sold by Coulter, Inc. Mean volume weighted diameter is the sum of the mass of each particle times the diameter of a spherical particle of equal mass and density, divided by total particle mass.
The term "glass transition temperature" or "T g " as used herein means the temperature at which a polymer changes from a glassy state to a rubbery state. This temperature (T g ) can be measured by differential thermal analysis as disclosed in "Techniques and Methods of Polymer Evaluation", Vol. 1, Marcel Dekker, Inc., N.Y., 1966.
The term "melting temperature" or "T m " as used herein means the temperature at which a polymer changes from a crystalline state to an amorphous state. This temperature (T m ) can be measured by differential thermal analysis as disclosed "Techniques and Methods of Polymer Evaluation".
The term "onset of fusing temperature" as used herein is relation to a toner powder means the lowest temperature at which a high density solid area patch developed with this toner exhibits good adhesion to paper as determined by the adhesion index and crack and rub tests. The crack and rub test involves fusing a toner patch onto paper, folding the patch and brushing the loose toner away, and evaluating the width of the crack. The adhesion index test involves adhering a metal block to a toner patch and measuring the energy required to cause interfacial failure between the toner layer and its contacting substrate by collision of a pendulum with the metal block. The term "ester compatibility" as used herein has reference to the capacity of a thermoplastic polymer, such as one usable in the manufacture of toner powders, to blend with an additive material which is an ester group containing quaternary ammonium salt compound.
(B) Quaternary Ammonium Salts
This invention is directed to quaternary ammonium salts of the formula: ##STR1## wherein R 1 is alkyl, aryl, and ##STR2## where R 5 is arylene or alkylene;
R 2 is alkyl, aryl or aralkyl or alkylene;
R 3 is alkyl, aryl, aralkyl or ##STR3## R 4 is alkyl, aryl or aralkyl; X is (CH 2 ) n or arylene;
Z.sup.⊖ is an anion; and
n is an integer from 2 to 6.
As used herein, the term "alkyl" includes straight and branched chain alkyl groups and cycloalkyl groups.
As used herein, the term anion refers to negative ions such as m-nitrobenzenesulfonate, tosylate, tetraphenylborate, dicyanamide, chloride, etc.
As used herein, the term aryl includes phenyl, naphthyl, anthryl and the like.
As used herein, the term arylene includes phenylene, naphthalene, and the like.
As used herein, the term aralkyl includes benzyl, naphthylmethyl and the like.
Alkyl and aryl groups can be unsubstituted or substituted with a variety of substituents such as alkoxy, halo or other groups.
Presently preferred quaternary ammonium salts are those of the formula ##STR4## wherein R 1 is cyclohexyl or phenyl;
R 2 and R 3 are methyl;
R 4 is benzyl;
Z.sup.⊖ is m-nitrobenzenesulfonate; and
n is 2.
The quaternary ammonium salts of the present invention can also be pendant groups from polymeric backbones in which case R 1 has the formula: ##STR5## wherein R 6 is hydrogen or alkyl and x is >1.
(C) Synthesis
Compounds of Formula (1) can be prepared by any convenient route. One general route is to acylate a N,N-di(lower alkyl) amino lower alkanol with an acid chloride to produce the corresponding (N,N-di(lower alkyl)amino) alkyl esters which are subsequently quaternized with a reactive aliphatic or aromatic halide. The quaternary ammonium compound is converted to the desired anion by a metathesis or ion exchange reaction with a reactive alkali metal aryl sulfonate or other acid salt.
Preferably, the acid chloride is either benzoyl chloride or cyclohexanecarbonylchloride, while the hydroxylamine is either 2-(N,N-dimethyl)aminoethanol or N-methyldiethanolamine. In place of the acid chloride, the corresponding carboxylic acid can be employed.
One convenient and presently preferred procedure for such an ester preparation is to prepare a basic aqueous solution of the tertiary amino alkanol. To this solution is slowly added a solution of the acid chloride in a water immiscible organic solvent, methylene chloride being presently preferred. The addition is preferably accompanied by rapid stirring. The mole ratio of aminoalkanol to total added acid chloride is preferably about 1:1. The ensuing reaction is exothermic, and, after the reaction is complete, stirring is preferably continued for a time period, such as at least about 1/4 hour. The organic layer is then separated, washed with water and dried, preferably over MgSO 4 or the like, and concentrated. The product is typically an oil which can be purified by distillation.
One convenient and presently preferred procedure for the preparation of the quaternary ammonium compound is to separately prepare the ester and the quaternizing agent as solutes in the same highly polar solvent, acetonitrile being one presently particularly preferred example. The mole ratio of quaternary ammonium compound to the quaternizing agent is preferably about 1:1. Such a solution is then heated at reflux for a time in the range of about 1 to about 2 hours. The reaction mixture is then concentrated by solvent evaporation to yield a viscous oil or a crystalline solid. The product can be used without further purification for the next step in the syntheses, or the product can be purified by recrystallization, for example, from a ketone, such as 2-butanone, or the like, followed by washing and drying.
One convenient and presently preferred procedure for preparation of the quaternary ammonium organic salt from the intermediate halide is to dissolve the ion exchange agent in an aqueous solution. To this solution is added a second aqueous solution containing the quaternary ammonium salt intermediate. The mole ratio of such salt to such ion exchange agent should be about 1:1. Typically, a precipitate is formed immediately which is in the form of an oil. This precipitate is collected, water washed (preferably with distilled or deionized water), and then dissolved in a water immiscible organic solvent, such as methylene dichloride, or the like. The water layer is separated, the organic layer is dried over MgSO 4 , or the like, and the product thereby concentrated. The resulting product can be recrystallized from an alkanol, such as isopropanol, or the like, or a ketone, such as 2-butanone, or the like, if desired.
(D) Toners And Toner Preparation
The quaternary ammonium salts of the present invention are incorporated into toner particles. For present purposes, toner particles can be regarded as being preferably comprised on a 100 weight percent basis of:
(a) about 0.5 to about 10 weight percent of at least one quaternary ammonium salt;
(b) about 75 to about 97.5 weight percent of a thermoplastic polymer; and
(c) about 2 to about 15 weight percent of a colorant.
The size of the toner particles is believed to be relatively unimportant from the standpoint of the present invention; rather the exact size and size distribution is influenced by the end use application intended. So far as now known, the toner particles of this invention can be used in all known electrophotographic copying processes. Typically and illustratively, toner particle sizes range from about 0.5 to about 100 microns, preferably from about 4 to about 35 microns.
The properties of a thermoplastic polymer employed as a toner matrix phase can vary widely. Typically and preferably, toner polymers have a glass transition temperature in the range of about 50° to about 120° C. and a melting temperature in the range of about 65° to about 200° C. Preferably, such a polymer has a number average molecular weight in the range of about 1,000 to about 10,000. The weight average molecular weight can vary, but preferably is in the range of about 10 4 to about 10 6 . Typical examples of such polymers include polystyrene, polyacrylates, polyesters, polyamides, polyolefins, polycarbonates, phenol formaldehyde condensates, alkyl resins, polyvinyldene chlorides, epoxy resins, various copolymers of the monomers used to make these polymers, such as polyesteramides, acrylonitrile copolymers with monomers, such as styrene, acrylics, and the like.
Preferably, thermoplastic polymers used in the practice of this invention are substantially amorphous. However, mixtures of polymers can be employed, if desired, such as compatible mixtures of substantially amorphous polymers with substantially crystalline polymers.
Presently preferred polymers for use in toner powders are polyesters. The structure of the polyester polymer can vary widely, and mixtures of different polyesters can be employed. Polyesters and methods for making such are generally known to the prior art. One presently more preferred polyester is polyethylene terephthalate, such as polyethylene terephthalate having an inherent viscosity in the range of about 0.25 to about 0.35 in methylene chloride solution at a concentration of about 0.25 grams of polymer per 100 milliliters of solution. In general, preferred polyesters have a glass transition temperature (T g ) in the range of about 50° to about 120° C. and a melting temperature (T m )in the range of about 65° to about 200° C.
An optional but preferred starting material for inclusion in such a blend is a colorant (pigment or dye). Suitable dyes and pigments are disclosed, for example, in U.S. Pat. No. 31,072, and in U.S. Pat. Nos. 4,140,644; 4,416,965; 4,414,152; and 2,229,513. One particularly useful colorant for the toners to be used in black and white electrophotographic copying machines is carbon black. When employed, colorants are generally employed in quantities in the range of about 1 to about 30 weight percent on a total toner powder weight basis, and preferably in the range of about 1 to about 8 weight percent.
The quaternary ammonium salts of the present invention are compatible with conventional charge control agents and other toner additives. If desired, a conventional charge control agent can be additionally incorporated into a toner particle composition. Examples of such charge control agents for toner usage are described in, for example, U.S. Pat. Nos. 3,893,935; 4,079,014; 4,323,634; and British Patent Nos. 1,501,065 and 1,420,839. If used, charge control agents are preferably employed in small quantities, such as an amount in the range of about 0.1 to about 5 weight percent on a total toner composition weight basis, and preferably in the range of about 0.1 to about 3 weight percent.
Toner compositions, if desired, can also contain other additives of the types which have been heretofore employed in toner powders, including leveling agents, surfactants, stabilizers, and the like. The total quantity of such additives can vary. A present preference is to employ not more than about 10 weight percent of such additives on a total toner powder composition weight basis.
Various procedures are known to the art for incorporating additives, such as the quaternary ammonium salts of the present invention, colorants, or the like, into a desired polymer. For example, a preformed mechanical blend of particulate polymer particles, quaternary ammonium salts, colorants, etc., can be roll milled or extruded at a temperature above the melt blending temperature of the polymer to achieve a uniformly blended composition. Thereafter, the cooled composition can be ground and classified, if desired, to achieve a desired toner powder size and size distribution.
Preferably, prior to melt blending, the toner components, which preferably are preliminarily placed in a particulate form, are blended together mechanically. With a polymer having a T g or a T m within the ranges above indicated, a melt blending temperature in the range of about 90° to about 160° C. is suitable using a roll mill or extruder. Melt blending times (that is, the exposure period for melt blending at elevated temperatures) are in the range of about 1 to about 60 minutes. After melt blending and cooling, the composition can be stored before being ground. Grinding can be carried out by any convenient procedure. For example, the solid composition can be crushed and then ground using, for example, a fluid energy or jet mill, such as described in U.S. Pat. No. 4,089,472. Classification, if employed, can be conventionally accomplished using one or two steps.
In place of melt blending, the polymer can be dissolved in a solvent and the additives dissolved and/or dispersed therein. Thereafter, the resulting solution or dispersion can be spray dried to produce particulate toner powders.
Limited coalescence polymer suspension procedures, are particularly useful for producing small sized, uniform toner particles, such as toner particles under about 10 microns in size.
Toner powders of this invention preferably have a fusing latitude temperature in the range of about 275° to about 400° F., although toner powders with higher and lower fusing temperatures can be prepared and used. Toner powders of this invention characteristically display excellent paper adhesion characteristics. Typically, toner powders of this invention have a paper adhesion index value in the range of about 30 to about 100, although toner powders with lower such values can be prepared and used. Paper adhesion index values of toner powders of this invention are characteristically higher than those of toner powders prepared with the same polymer and additives but not containing a quaternary ammonium salt of this invention.
When the polymer employed in a toner powder of this invention is a polyester, the ester group containing quaternary ammonium salts used in this invention display superior ester compatibility therewith.
The invention is further illustrated by the following Examples. In these Examples, all melting points and boiling points are uncorrected. NMR (nuclear magnetic resonance) spectra were obtained with a Varian Gemini-200 NMR spectrometer. All elemental analyses were performed by mass spectroscopy. Unless otherwise indicated, all starting chemicals were commercially obtained.
EXAMPLE 1
2-(N,N-Dimethylamino)ethyl 4-methylvalerate
A solution of 67.31 g (0.50 mol) of 4-methylvaleryl chloride in 300 ml of methylene chloride was added to a solution of 44.57 g (0.50 mol) of 2-dimethylaminoethanol, 20.0 g (0.50 mol) of sodium hydroxide and 300 ml of water in a stream via a dropping funnel while maintaining rapid stirring. The reaction was exothermic and was stirred for an additional 20 minutes. The organic layer was then separated, washed with water, dried over MgSO 4 and concentrated to an oil. Distillation of the oil gave 56.8 g of product; bp=70° C./0.80 mm.
Anal.Calcd. for C 10 H 21 NO 2 : C,64.13;H,11.30;N,7.48; Found: C,59.78;H,10.94;N,6.51.
EXAMPLE 2
2-(N,N-Dimethylamino)ethyl benzoate
A solution of 70.29 g (0.50 mol) of benzoyl chloride in 500 ml of methylene chloride was added to a solution of 44.57 g (0.50 mol) of 2-dimethylaminoethanol, 20.0 g (0.50 mol) of sodium hydroxide and 500 ml of water over 15 minutes with rapid stirring. Stirring was continued for 3.25 hours after which the organic layer was separated, washed with water, dried over MgSO 4 and concentrated. Distillation of the residue gave 59.5 g of product; bp=102°-8° C./0.50 mm.
Anal.Calcd. for C 11 H 15 NO 2 : C,68.37;H,7.82;N,7.25; Found: C,66.11;H,7.89;N,7.25.
EXAMPLE 3
2-(N,N-Dimethylamino)ethyl 2-ethyl hexanoate
The title compound was prepared by the procedure of Example 1.
EXAMPLE 4
2-(N,N-Dimethylamino)ethyl cyclohexanoate
The title compound was prepared by the procedure of Example 1.
EXAMPLE 5
2-(N,N-Dimethylamino)ethyl myristate
A solution of 91.35 g (0.40 mol) of myristic acid, 35.7 g (0.40 mol) of 2-dimethylaminoethanol, 0.5 g of p-toluenesulfonic acid and a suitable volume of toluene was heated at reflux for approximately 48 hours in a 1-neck 3 liter flask equipped with Dean-Stark trap and condenser. At the end of this time, 7.0 ml of water had collected in the trap. The solution was cooled, stirred with K 2 CO 3 , filtered and concentrated. The residue was distilled to give 75.0 g of product; bp=145°-50° C/0.050 mm.
EXAMPLE 6
2-(N,N-Dimethylamino)ethyl 4-chlorobenzoate
The title compound was prepared by the procedure of Example 1.
EXAMPLE 7
2-(N,N-Dimethylamino)ethyl 4-methoxybenzoate
The title compound was prepared by the procedure of Example 1.
The acid or acid chloride starting materials and the analytical data for the ester products are shown in Table I below for Examples 1-7.
TABLE I__________________________________________________________________________2-(N,N-DIMETHYLAMINO) ETHYL ESTERS ##STR6## AnalysesEx. Starting acid Or Calcd FoundNo. Acid Chloride Identity of R.sub.1 bp, C/mm C H N Cl C H N Cl__________________________________________________________________________1 4-methyl- (CH.sub.3).sub.2 CHCH.sub.2 CH.sub.2 70/0.8 64.13 11.30 7.48 59.78 10.94 6.51 valeroyl chloride2 benzoyl chloride ##STR7## 102-8/0.5 68.37 7.82 7.25 66.11 7.89 7.253 2-ethyl CH.sub.3 (CH.sub.2).sub.3 CH(C.sub.2 H.sub.5) 75-8/0.75 66.9 11.7 6.5 65.4 10.8 6.3 hexanoyl chloride4 cyclohexane- carbonyl chloride ##STR8## 78/0.65 88-9/0.50.sup.(1) 66.29 66.29 10.62 10.62 7.03 7.03 64.51 66.38 10.07 10.99 7.20 7.495 myristic acid CH.sub.3 (CH.sub.2).sub.12 145-50/0.5 72.19 12.45 4.68 72.34 12.06 3.986 4-chlorobenzoyl chloride ##STR9## 122-8/0.50 58.03 6.20 6.15 15.57 57.50 6.29 6.0 14.847 4-methoxy benzoyl chloride ##STR10## 128-40/0.30 64.55 7.67 6.27 64.59 7.46 6.13__________________________________________________________________________ .sup.(1) intermediate ester distilled twice before analysis
EXAMPLE 8
N-(4-Methylvaleryloxyethyl)-N,N-dimethylbenzylammonium chloride
A solution of 46.83 g (0.25 mol) of 2-(N,N-dimethylamino)ethyl-4-methylvalerate (prepared as described in Example 1) and 31.65 g (0.25 mol) of benzyl chloride in 250 ml of acetonitrile was heated at reflux for 1.25 hours. The reaction mixture was then concentrated to a viscous oil and used in the ion exchange step with no further purification.
EXAMPLE 9
N-(Benzoyloxyethyl)-N,N-dimethylbenzylammonium chloride
A solution of 57.96 g (0.30 mol) of 2-(N,N-dimethylamino)ethyl benzoate (prepared as described in Example 2), 37.98 g (0.30 mol) of benzyl chloride and 500 ml of acetonitrile was heated at reflux for 2 hours. The reaction mixture was concentrated to a white solid which was then washed with ether and recrystallized from acetonitrile. The yield of product was 69.0 g; mp=164°-6° C.
EXAMPLE 10
N-(2-Ethylhexanoyloxyethyl)-N,N-dimethylbenzylammoniumchloride
The title compound was prepared by the procedure of Example 8.
EXAMPLE 11
N-(Cyclohexanoyloxyethyl)-N,N-dimethylbenzylammonium chloride
The title compound was prepared by the procedure of Example 8.
EXAMPLE 12
N-(Myristyloxyethyl)-N,N-dimethylbenzyl-ammonium chloride
The title compound was prepared by the procedure of Example 8.
EXAMPLE 13
N-(4-Chlorobenzoyloxylethyl)-N,N-dimethylbenzylammonium chloride
The title compound was prepared by the procedure of Example 9.
EXAMPLE 14
N-(4-Methocybenzolyoxyethyl)-N,N-dimethylbenzylammonium chloride
The tile compound was prepared by the procedure of Example 9.
The ester starting materials and the analytical date for the quaternary ammonium chloride products are shown in Table II below for Examples 8-14.
TABLE II__________________________________________________________________________N-(2-ACYLOXYETHYL)-N,N-DIMETHYLBENZYLAMMONIUM CHLORIDES* ##STR11## AnalysesEx. Calcd FoundNo. Identity of R.sub.1 mp, C C H N Cl C H N Cl__________________________________________________________________________ 8 (CH.sub.3).sub.2 CHCH.sub.2 CH.sub.2 oil 9 ##STR12## 164-610 CH.sub.3 (CH.sub.2).sub.3 CH(C.sub.2 H.sub.5) oil11 ##STR13## oil12 CH.sub.3 (CH.sub.2).sub.12 oil13 ##STR14## 196 dec 61.03 5.97 3.95 20.01 60.63 5.86 4.02 20.0514 ##STR15## 195-6 dec 65.23 6.91 4.00 10.13 64.97 6.77 4.13 11.43__________________________________________________________________________ *Quaternizing agent was benzyl chloride
EXAMPLE 15
N-(4-Methylvaleryloxyethyl)-N,N-dimethylbenzylammonium m-nitrobenzenesulfonate
A hot solution (300 ml) of 56.29 g (0.25 mol) of sodium m-nitrobenzenesulfonate in water was added to a solution (300 ml) of 78.48 g (0.25 mol) of N-(4-methylvaleryloxyethyl)-N,N-dimethylbenzylammonium chloride prepared as described in Example 8) in water. An oily precipitate formed immediately which crystallized on cooling. The solid was collected, washed with water and dissolved in methylene chloride. The water layer was separated and the organic layer was dried over MgSO 4 and concentrated. Recrystallization of the solid residue from isopropanol gave 81.6 g of product; mp=106°-8° C. Anal.Calcd. for C 23 H 32 N 2 O 7 ; C,57.84;H,6.71;N,5.83;S,6.67; Found: C,57.26;H,6.53;N,5.90;S,6.85.
EXAMPLE 16
N-(Benzoyloxyethyl)-N,N-dimethylbenzylammonium m-nitrobenzenesulfonate
A solution of 45.03 g (0.20 mol) of sodium m-nitrobenzenesulfonate in 200 ml of water was added to a solution of 63.97 g (0.20 mol) of N-(benzoyloxyethyl)-N,N-dimethylbenzylammonium chloride (prepared as described in Example 9) in 250 ml of water. An oily precipitate immediately formed. The water was decanted from the oil and fresh water was added. After standing overnight, the oil was taken up in methylene chloride. The water layer was separated and the organic layer was dried over MgSO 4 and concentrated to an oil which crystallized. The solid was recrystallized from 2-butanone, collected, washed with ether and dried. The yield of product was 36.0 g; mp=104°-6° C.
Anal.Calcd for C 24 H 26 N 2 O 7 S C,59.25;H,5.39;N,5.76;S,6.59; Found: C,58.90;H,5.34;N,5.62;S,6.76.
EXAMPLE 17
N-(2-Ethylhexanoyloxyethyl)-N,N-dimethylbenzylammonium m-nitrobenzenesulfonate
The title compound was prepared by the procedure of Example 16.
EXAMPLE 18
N-(cyclohexanoyloxyethyl)-N,N-dimethylbenzylammonium m-nitrobenzenesulfonate
The title compound was prepared by the procedure of Example 16.
EXAMPLE 19
N-(myristyloxyethyl)-N,N-dimethylbenzylammonium m-nitrobenzenesulfonate
The title compound was prepared by the procedure of Example 16.
EXAMPLE 20
N-(4-chlorobenzoyloxyethyl)-N,N-dimethylbenzylammonium m-nitrobenzenesulfonate
The title compound was prepared by the procedure of Example 16.
EXAMPLE 21
N-(4-methoxybenzoyloxyethyl)-N,N-dimethylbenzylammonium m-nitrobenzenesulfonate
The title compound was prepared by the procedure of Example 16.
The quaternary ammonium chloride starting materials and the analytical data for the quaternary ammonium m-nitrobenzenesulfonate salt products are shown in Table III below for Examples 15-21.
TABLE III__________________________________________________________________________N-(2-ACYLOXYETHYL)-N,N-DIMETHYLBENZYLAMMONIUM M-NITROBENZENESULFONATES* ##STR16## AnalysesEx. Calcd FoundNo. Identity of R.sub.1 mp, C C H N Cl S C H N Cl S__________________________________________________________________________15 (CH.sub.3).sub.2 CHCH.sub.2 CH.sub.2 106-8 57.48 6.71 5.83 6.67 57.26 6.53 5.90 6.8516 ##STR17## 104-6 59.25 5.39 5.76 6.59 58.90 5.34 5.62 6.7617 CH.sub.3 (CH.sub.2).sub.3 CH(C.sub.2 H.sub.5) -- 59.04 7.13 5.51 6.30 59.32 7.02 5.48 6.3118 ##STR18## 97-9 58.5 6.54 6.51 6.51 58.5 6.39 6.58 6.5819 CH.sub.3 (CH.sub.2).sub.12 54-7 62.81 8.16 4.73 5.41 63.27 8.36 4.09 4.5420 ##STR19## 123.5-125.5 55.33 4.84 5.38 6.80 6.15 55.45 4.87 5.20 7.39 6.3021 ##STR20## 152-153 58.13 5.46 5.42 6.21 58.18 5.56 5.42 6.71__________________________________________________________________________ *low exchange agent was sodium mnitrobenzenesul fonate
EXAMPLE 22
N,N-Bis(2-cyclohexanoyloxyethyl)methylamine
A solution of 73.31 g (0.05 mol) cyclohexanecarbonyl chloride in 200 ml of methylene chloride was added to a solution of 29.79 g (0.25 mol) of N-methyldiethanolamine, 20.0 g (0.50 mol) of sodium hydroxide and 200 ml of water over approximately 1 minute. The reaction was exothermic requiring the use of a reflux condenser. The reaction mixture was stirred for another 45 minutes after which the organic layer was separated, washed with water, dried over MgSO 4 and concentrated. The residue was distilled to give product, bp=192°-9° C./0.30 mm.
Anal. Calcd for C 19 H 33 NO 4 : C,67.22;H, 9.80;N,4.13; Found: C,67.45;H,10.05;N,4.31.
EXAMPLE 23
N,N-Bis(2-cyclohexanoyloxyethyl)-N-methylbenzylammonium chloride
A solution of 28.5 g (0.084 mol) of N,N-bis(2-cyclohexanoyloxyethyl)methylamine (prepared as described in Example 22), 10.63 g (0.084 mol) of benzyl chloride and 200 ml of acetonitrile was heated at reflux for 2.5 hours and concentrated to an oil. Ether was added to the oil which induced crystallization. The white solid was collected, washed two times with ether and recrystallized from 2-butanone. The yield of product was 8.3 g; mp=143.5°-4.5° C.
Anal.Calcd for C 26 H 40 C1NO 4 : C,67.01;H,8.65;C1,7.61;N,3.01; Found: C,66.86;H,8.51;C1,7.51;N,2.93.
EXAMPLE 24
N,N-Bis(2 cyclohexanoyloxyethyl)-N-methyl-benzylammonium m-nitrobenzenesulfonate
A solution of 3.38 g (0.015 mol) of sodium m-nitrobenzenesulfonate in 15 ml of water was added to a solution of 7.0 g (0.015 mol) of N,N-bis(2-cyclohexanonyloxyethyl)-N-methylbenzylammonium chloride (prepared as described in Example 23) in 50 ml of water. An oily precipitate immediately formed. The oil was rinsed twice with water, dissolved in methylene chloride, dried over MgSO 4 and concentrated. The resultant oil was crystallized with P-513 ligroine and warmed. The crystals were collected, washed with ether, dried and recrystallized from 2-butanone. The yield of product was 2.64 g; mp=123°-4.5° C.
Anal. Calcd for C 23 H 44 N 2 O 9 S: C,60.74;H,7.01;N,4.43;S,5.0; Found: C,60.37;H,6.93;N,4.34;S,5.17.
EXAMPLE 25
Bis(2-dimethylaminoethyl) terephthalate
A solution of 40.60 g (0.20 mol) of terephthaloyl chloride in 200 ml methylene chloride was gradually added to a solution of 35.66 g (0.40 mol) of 2-dimethylaminoethanol, 16.0 g (0.40 mol) of sodium hydroxide and 200 ml of water and stirred rapidly. The reaction was exothermic and achieved reflux. The mixture was stirred for another 1.75 hours after which the organic layer was separated, washed with water, dried over MgSO 4 and concentrated to an oil.
Anal. Calcd for C 16 H 24 N 2 O 4 ; : C,62.32;H,7.84;N,9.08; Found: C,60.74;H,8.56;N,9.5.
EXAMPLE 26
Bis(2-(N,N-dimethylbenzylammonium)ethyl) terephthalate dichloride
A solution of 30.84 g (0.10 mol) of bis(2-dimethylaminoethyl) terephthalate and 25.32 g (0.20 mol) of benzyl chloride was heated on a steam bath. Within a few minutes, the mixture solidified. The resultant caked solid was washed with acetonitrile and used in the next step without further purification.
EXAMPLE 27
Bis(2-(N,N-dimethyl benzylammoniumethyl) terephthalate bis-(m-nitrobenzenesulfonate)
A solution of 56.16 g (0.01 mol) of the crude bis(2-N,N-dimethylbenzylammonium)ethyl)terephthalate prepared as described in Example 26 in 200 ml of water was added to a solution of 45.02 g (0.20 mol) of sodium m-nitrobenzenesulfonate in 200 ml of water. An oily precipitate immediately formed. The aqueous phase was decanted and the residue was washed several times with water. Ethyl acetate was added to the oil and after standing the oil crystallized. The solid was collected, washed with ether and recrystallized twice from acetonitrile to give 32.7 g (36.5%) of a product whose melting point was 170°-1° C.
Anal. Calcd for C 42 H 46 N 4 O 14 S 2 : C,56.37;H,5.18;N,6.26;S,7.17; Found: C,56.13;H,5.05;N,6.21;S,7.57.
EXAMPLE 28
Poly(2-dimethylaminoethyl methacrylate)
A solution of 50.0 g (0.318 mol) of N,N-dimethylaminoethyl methacrylate in 450 g of DMF was purged with nitrogen. Azobisisobutyronitrile (0.50 g) was added and the solution was heated in a 60° C. bath for 53.6 hours. The resultant polymer was used in the next step without isolation.
EXAMPLE 29
Poly(2-(N,N-dimethyl aminobenzylammonium)ethyl methacrylate chloride)
The solution of poly(2-dimethylaminoethyl methacrylate) prepared in the preceding Example 28 in dimethylforamide was treated with 40.26 g (0.318 mol) of benzyl chloride and heated under nitrogen in a 60° C. bath for 4 hours. A viscous oil precipitated and was allowed to stand for 10 days. Acetone was added to the mixture to harden the polymer which was then collected and used in the next step with no further purification.
EXAMPLE 30
Poly(2-(N,N-dimethylbenzyl ammonium)ethyl methacrylate m-nitrobenzenesulfonate)
The poly(2-(N,N-dimethylaminobenzylammonium)ethyl methacrylate chloride prepared in the preceding Example 29 was dissolved in 1 liter of water and to it was added a solution of 71.6 g (0.318 mol) of sodium m-nitrobenzenesulfonate in 500 ml of water. A polymer immediately precipitated. The aqueous phase was decanted and the polymer was allowed to stand overnight in water. The water was decanted and the polymer was washed with acetone and then ether, and finally dried. The polymer was dissolved in DMF and reprecipitated into ether. The gummy precipitate was isolated, washed again with ether and dried. The structure was confirmed by NMR although the polymer was strongly contaminated with DMF.
EXAMPLES 30-33
The procedure for Example 16 is repeated except that, in place of sodium m-nitrobenzenesulfonate, one equivalent of each of the ion exchange salts shown in the following Table IV in such an aqueous solution is added to the starting quaternary ammonium chloride solution. The structure of the cation formed in, and the melting point of, each salt so recovered and recrystallized is shown in Table IV. For comparison purposes, the melting point of the product of Example 16, and the melting point of the starting compound of Example 8 are included in Table IV.
TABLE IV______________________________________N-(2-BENZOYLOXYETHYL)-N,N-DIMETHYLBENZYLAMMONIUM SALTS ##STR21##Starting IonEx. Exchange Identity of Y.sup.- MeltingNo. Agent in Formula Point °C.______________________________________ 8 Cl.sup.⊖ 170-17216 sodium m-nitrobenzene- sulfonate ##STR22## 104-631 sodium tetraphenyl- borate ##STR23## 194-632 sodium dicyanamide ⊖N(CN).sub.2 (amorphous)33 sodium p-toluenesulfonate ##STR24## 110-112______________________________________
EXAMPLES 34-36
Toner Powder Preparation
An amorphous branched polyester comprised of a condensate of dimethylterephthalate (87 mole %), dimethylglutarate (13 mole %), 1,2-propanediol (95 mole %) and glycerol (5 mole %) having a T g of 63° C. and a number average molecular weight of about 3000 was prepared using a conventional polycondensation technique. This polymer was preliminarily ground into particles having a size in the range of about 1/16", and such particles are blended with various additives as individually identified in the following Table V to produce various blends as shown in such Table.
TABLE V__________________________________________________________________________Toner Composition (Dry Weight Basis) Blend Blend BlendComponent Ex. 34 Ex. 35 Ex. 36ID No. Component wt %.sup.5 pph.sup.6 wt %.sup.5 pph.sup.6 wt %.sup.5 pph.sup.6__________________________________________________________________________1 Polyester 90.66 100.0 91.74 100.0 90.66 100.02 Carbon Black.sup.3 4.53 5.0 4.59 5.0 4.53 5.03 LSA.sup.4 3.63 4.0 3.67 4.0 3.63 4.04 Charge Control Agent 1.18.sup.1 1.3 (none) (none) 1.18.sup.2 1.3TOTAL 100 110.3 100 109.0 100 110.3__________________________________________________________________________ Table V Footnotes: .sup.1 Charge Control Agent ##STR25## - .sup.2 The charge control agent was the compound identified in Example 16 above. .sup.3 The carbon black was "Regal ™ 300" obtained commercially from Cabot Corporation. .sup.4 The LSA was a polyester/polydimethylsiloxane block copolymer as described in U.S. Pat. No. 4,758,491. .sup.5 Weight percent on a total blend composition basis. .sup.6 Parts by weight.
Each blend was rolled milled at 130° C. for 12 minutes, cooled, crushed, ground and classified to produce a toner powder product having a size of about 12 microns and a size distribution of about 2-30 microns.
EXAMPLES 37-41
Toner Powder Preparation
The polyester used in Examples 34-36 was additionally compounded with various additives as individually identified in the following Table VI.
TABLE VI______________________________________Toner Composition (Dry Weight Basis)Component ConcentrationID. No. Component Parts______________________________________1 polyester 1002 carbon black 53 LSA 24 Charge Control Agent -- (formulation Ex. 37) 1.50 (formulation Ex. 38) .75 (formulation Ex. 39) 1.50 (formulation Ex. 40) 2.25 (formulation Ex. 41) 1.50______________________________________
The carbon black was "Regal™ 300" as in Examples 34-36. The LSA was the same as in Examples 34-36. The charge control agent used for the formulation of Example 37 was the same as used in Example 34. The charge control agent used in each of formulation Examples 38, 39, and 40 was the compound identified in Example 18 above. The charge control agent used in formulation of Examples 41 was the compound identified in Example 16 above. The charge control agent of formulation Example 37 was utilized for comparative purposes.
Each of such five formulations was extruded in a twin screw extruder.
The product so extruded was cooled, crushed, and ground to produce toner powders each having a size of about 12 microns and a size distribution of about 2-30 microns.
EXAMPLE 42
(Comparative) Toner Powder Preparation
Using a polyester such as described in Examples 34-36, the following formulation was compounded.
TABLE VII______________________________________Toner Composition (Dry Weight Basis)Component ConcentrationID. No. Component pph______________________________________1 polyester 1002 carbon black 53 Charge Control Agent 1.5______________________________________
The carbon black was "Regal™ 300" as in Examples 34-36. The charge control agent was methyltriphenyl phosphonium tosylate.
This blend was extruded on a twin screw extruder cooled, crushed, ground and classified to produce a toner powder.
EXAMPLES 43-44
Toner Powder Preparation
The polyester described in Examples 34-36 was additionally compounded with various additives as individually identified in the following Table VIII.
TABLE VIII______________________________________Toner Composition (Dry Weight Basis) Blend Comp. Blend Comp.Component Ex. 43 Ex. 44ID. No. Component pph pph______________________________________1 polyester 100 1002 yellow pigment 3 33 Charge control agent A 1.5 B 1.5______________________________________
Charge control agent A was that used in Example 34; this charge control agent and the formulation of Example 44 were utilized for comparative purposes. Charge control agent B was the compound identified in Example 16 above.
Each blend was roll milled on the same roll mill as used in Examples 35-37, cooled, crushed, ground and classified to produce a toner powder product.
EXAMPLES 45-48
Toner Powder Preparation
A styrene butylacrylate copolymer was obtained by limited coalescence polymerizaton and blended with various additives as identified in the following TABLE IX.
TABLE IX______________________________________Toner Composition (Dry Weight Basis)Component ConcentrationID No. Component pph______________________________________1 Styrene butylacrylate 100 copolymer2 Carbon black 33 Charge Control Agent Formulation of Ex. 45 1 Formulation of Ex. 46 1 Formulation of Ex. 47 2 Formulation of Ex. 48 1______________________________________
The carbon black was "Regal™ 300" as in Examples 34-36. The charge control agent used for the formulation of Example 45 was as in Example 34. The formulation of Example 45 was utilized for comparative purposes. The charge control agent used for the formulation of Examples 46 and 47 was the compound identified in Example 18 above. The charge control agent used for the formulation of Example 48 was the compound identified in Example 16 above.
Each of such formulations was roll milled, cooled, crushed, ground and classified to produce a toner powder product.
EXAMPLE 49
Toner T g
To determine if the quaternary ammonium salt compounds were plasticizing the toner and thereby affecting fusing, the T g of each of the toner powders of Examples 37-41 above was measured. The results were shown in the following Table X.
TABLE X______________________________________Toner Glass Transition Temperature Toner ID T.sub.g Ex. No. (°C.)______________________________________ 37 60.6 38 62.2 39 61.8 40 60.9 41 60.8______________________________________
Since this data shows that the toner powders
containing the compounds of Examples 16 and 18 had T g values which were equivalent to or slightly above, the T g value for a toner powder containing the charge agent of Example 34, it was concluded that the quaternary ammonium salt compounds are not acting as plasticizers in toner particles.
EXAMPLE 50
Fusing And Adhesion
Each of the polyester-based toner powders of Examples 34-36 was evaluated on a fusing breadboard consisting of a fusing roller coated with a fluorocarbon elastomer (available commercially under the designation Viton™ from E. I. du Pont de Nemours & Co.) engaged at constant speed and pressure onto a backup roller coated with a polytetrafluorethylene (available commercially as Silverstone™ from E. I. duPont de Nemours & Co. Both rollers had their circumferential surfaces coated by hand using a release oil (available commercially under the designation "DC200 oil" from Dow Corning Company).
Six longitudinally extending stripes of toner were applied to various receiver sheets which were then run through the fusing breadboard.
The receiver sheets were:
(a) Husky™ paper, an acidic paper, available commercially from Weyerhauser Company;
(b) Kodak™ DP paper, available commercially from Eastman Kodak Company; and
(c) Hammermill™ 9000 DP, an alkaline paper available commercially from the Hammermill Company.
The adhesion index (A.I.) and crack width at various temperatures for each toner powder were determined and used as an indication of fusing performance. The results are shown for the Hammermill.
TABLE XI______________________________________Adhesion Index at Various TemperaturesTemperature Adhesion Index (AI) of Toner°F. Ex. 35 Ex. 37 Ex. 41______________________________________275 10 5 10300 5 10 20325 30 12 35350 62 30 80375 100 25 100______________________________________
The toner of Example 35 contained no charge agent, the toner of Example 37 contained the charge agent of Example 34 and the toner of Example 41 contained the charge agent of the invention identified in Example 16.
The toner of Example 37 (comparative) reached the minimum acceptable adhesion index (A.I.) value of 30 at 350° F. The toner of Example 35 (which contained no charge agent), and the toner of Example 41 containing the quaternary ammonium salt reached the minimum A.I. value at 325° and 315° F., respectively. The A.I. values are the average of 3 measurements and the standard deviation of the values is 10 A.I. units.
EXAMPLE 51
Fusing And Adhesion
Each of the styrene-butylacrylate-based toner powders of Examples 45-48 was evaluated on a fusing breadboard similarly to the procedure described in Example 50 except that the fusing roller was a Silverstone roller and the backup roller was a red rubber roller. No wicking oil was applied to the rollers.
The toner powders of Examples 45-48 reached the minimum A.I. of 30 at 365°, 320°, 310°, and 310° F., respectively (same standard deviation as in Example 50).
The average transmission density was between 0.8 and 1.2.
EXAMPLE 52
Crack and Rub
The crack and rub characteristics of the polyester based toners of Examples 34-36 were evaluated and the results are as shown in Table XII below:
TABLE XII______________________________________Crack and Rub AnalysisRef. Toner IDNo. Ex. No. 275° F. 300° F. 325° F. 350° F. 375° F.______________________________________A Example 35 poor- poor- poor+ fair- goodB Example 37 poor- poor poor poor+ fairC Example 41 poor- poor- poor+ good- good______________________________________
The toner powder of Ex. 35 (no charge agent) was comparable to the toner powder of Example 41 (containing the charge agent of Example 16), and they both had acceptable crack and rub performance at a lower temperature than the toner powder of Example 37.
EXAMPLE 53
Fusing And Adhesion
Each of the polyester based toner powders of Examples 37-42 was evaluated for fusing and adhesion performance using "Husky™" paper and the procedure of Example 50. The toner powder of Example 42 was included for comparison purposes.
The adhesion index (A.I.) at various temperatures for each toner powder is shown in Table XIII below.
TABLE XIII______________________________________Adhesion Index At Various TemperaturesTemperature Adhesion Index (A.I.) of Toner°F. Ex. 37 Ex. 38 Ex 39 Ex 40 Ex 41 Ex 42______________________________________325 21 38 20 21 23 14350 21 40 35 46 62 50375 25 83 100 83 100 100______________________________________
In Table XIII, the values shown are the average adhesion index value of three strips and the standard division of the A.I. measurements was between 0 and 10 units.
EXAMPLE 54
Crack and Rub
The procedure of Example 53 was repeated except that each of the polyester based toner powders of Examples 37-41 was evaluated using "Hammermill™ 9000 DP" alkaline paper. The results are shown in Table XIV below.
TABLE XIV______________________________________Crack and Rub AnalysisRef. Toner IDNo. Ex. No. Comment 325° F. 350° F. 375° F. 400° F.______________________________________A 37 poor poor poor fair-B 38 poor poor fair no dataC 39 poor poor fair- fair+D 40 poor fair- fair- goodE 41 poor fair fair good______________________________________
The foregoing specification is intended as illustrative and is not to be taken as limiting. Still other variations within the spirit and scope of the invention are possible and will readily present themselves to those skill in the art. | Toner particles comprising a polyester binder and a charge control agent are provided wherein such agent is a quaternary ammonium salt having one or more ester-containing moieties. Such an ester-containing salt causes toner particles to display lower fusing temperature, improved paper adhesion indexes, and improved polyester binder compatibility compared to nonesterified salts. | 6 |
RELATED APPLICATIONS
This application claims priority to U.S. Provisional Application Ser. No. 60/569,952, filed May 11, 2004 (pending) and U.S. Provisional Application Ser. No. 60/571,553, filed May 13, 2004, (pending), the disclosures of which are hereby incorporated by reference herein in their entireties.
BACKGROUND OF THE INVENTION
The invention relates to the treatment of autoimmune disorders.
Gastrointestinal microflora play a number of vital roles in maintaining gastrointestinal tract function and overall physiological health. Perturbations in gastrointestinal function are associated with the onset and progression of immune system disorders, including autoimmune disorders. Autoimmune disorders develop when the immune system mounts an immune response against normal body tissues. Normally, the immune system is capable of differentiating “self” from “non-self” tissue. Autoimmune disorders occur when the normal control process is disrupted. They may also occur if normal body tissue is altered so that it is no longer recognized as “self.” Microorganisms, such as pathogenic bacteria, fungi, and viruses, and other causes (drugs, alcohol, smoking, stress) trigger some of these changes, particularly in people with a genetic predisposition to an autoimmune disorder. Autoimmune disorders result in destruction of one or more types of body tissues, abnormal growth of an organ, or changes in organ function. The disorder may affect only one organ or tissue type or may affect multiple organs and tissues. Organs and tissues commonly affected by autoimmune disorders include blood components such as red blood cells, blood vessels, connective tissues, endocrine glands such as the thyroid or pancreas, muscles, joints, and skin.
Psoriasis is a chronic, genetically-influenced autoimmune disorder, most common in people in their 20s, 30s, and 40s. Psoriasis is rare under age 3. In the United States, two or three out of every 100 people suffer from psoriasis. Current topical psoriasis treatments use emollients, keratolytic agents, coal tar, anthralin, corticosteroids, and calpotriene. These approaches have variable efficacy, fail to prevent frequent relapses, and are often associated with adverse side effects. Current systemic treatments are usually reserved for patients with physically, socially, or economically disabling psoriasis that has not responded to topical treatment, and often include phototherapy and/or antifungal drugs, the latter of which can only be used for short periods of time due to toxicity and adverse side effects. Accordingly, there is a need for an effective systemic psoriasis treatment that avoids the disadvantages associated with current topical and systemic treatments.
SUMMARY OF THE INVENTION
The invention provides a method of reducing a symptom of psoriasis by identifying a patient suffering from or at risk of developing psoriasis and administering to the patient a composition that includes Bacillus coagulans bacteria. The composition is ingested by a human subject that has one or more symptoms of a dermatological disorder such as psoriasis. Bacterial species include Bacillus coagulans , e.g., Bacillus coagulans hammer, preferably Bacillus coagulans hammer strain Accession No. ATCC 31284, or one or more strains derived from Bacillus coagulans hammer strain Accession No. ATCC 31284 (e.g., ATCC Numbers: GBI-20, ATCC Designation Number PTA-6085; GBI-30, ATCC Designation Number PTA-6086; and GBI-40, ATCC Designation Number PTA-6087; see U.S. Pat. No. 6,849,256 to Farmer). Symptoms of psoriasis include scaling, blistering, skin lesions, itchiness, and pain (e.g., joint pain). In embodiments of the invention, the composition also includes a non-microbially derived antifungal agent (e.g., a member of the azole or pyrrole class of antifungal compounds such as clotrimazole, fluconazole, itraconazole, ketoconazole, miconazole, nystatin, terbinafine, terconazole, or tioconazole), an immunosuppressive agent (e.g., methotrexate, tacrolimus, cyclosporine, hydroxyurea, mycophenolate mofetil, sulfasalazine, or 6-thioguanine), a retinoid, or an antibiotic agent (e.g., gentamicin, vancomycin, oxacillin, tetracycline, nitroflurantoin, chloramphenicol, clindamycin, trimethoprim sulfamethoxasole, cefaclor, cefadroxil, cefixime, cefprozil, ceftriaxone, cefuroxime, cephalexin, loracarbef, ampicillin, amoxicillin clavulanate, bacampicillin, cloxicillin, penicillin VK, ciprofloxacin, grepafloxacin, levofloxacin, lomefloxacin, norfloxacin, ofloxacin, sparfloxacin, trovafloxacin, azithromycin, or rythromycin). Administration to the patient includes delivery of the composition(s) via the gastrointestinal tract. The gastrointestinal tract is the system of organs in a mammal including the mouth (buccal cavity), pharynx, esophagus and cardia, stomach(s), and intestines. The bacteria are administered at a dose that reduces a level of TNF-α in the patient.
Following oral administration, colonization of the gastrointestinal tract with Bacillus coagulans bacteria occurs between 24-48 hours. Continued colonization is improved by the repeated administration of Bacillus coagulans , such as daily administration. For example, a Bacillus coagulans bacteria-containing composition is administered (e.g., taken orally) about once every day for about 2, 3, 4, 5, 6, 7, 10, 15, 20, 25, 30, 45, 60, 75, 90, 100, 125 or more days. In embodiments of the invention the Bacillus coagulans bacteria are provided at a concentration of from about 1×10 8 to about 1×10 10 viable bacteria, e.g., at a concentration of from about 1×10 9 to about 2×10 9 viable bacteria. The Bacillus coagulans bacteria are provided in the form of spores and/or vegetative cells.
The invention also provides a method for the treatment of psoriasis by administering a first dose of a composition containing Bacillus coagulans bacteria at a first point in time, and administering a second dose of the composition at a second, subsequent point in time. The bacteria are, for example, Bacillus coagulans hammer or bacteria derived from Bacillus coagulans hammer strain Accession No. ATCC 31284; available to the public via the ATCC. The treatment includes treating a symptom of psoriasis (e.g., scaling, blistering, skin lesions, itchiness, and joint pain). Bacillus coagulans bacteria are provided at a concentration of from about 1×10 8 to about 1×10 1 ° viable bacteria, e.g., at a concentration of from about 1×10 9 to about 2×10 9 viable bacteria. The Bacillus coagulans bacteria are provided in the form of spores or vegetative cells. The composition includes a non-microbially derived antifungal agent, such as an azole, an organic five-membered ring compound containing one or more atoms in the ring. Exemplary azoles include clotrimazole, fluconazole, itraconazole, ketoconazole, miconazole, nystatin, terbinafine, terconazole, or tioconazole. The invention optionally includes administration of an immunosuppressive agent, such as methotrexate, cyclosporine, hydroxyurea, mycophenolate mofetil, sulfasalazine, or 6-thioguanine, or an antibiotic agent, such as gentamicin, vancomycin, oxacillin, tetracycline, nitroflurantoin, chloramphenicol, clindamycin, trimethoprim sulfamethoxasole, cefaclor, cefadroxil, cefixime, cefprozil, ceftriaxone, cefuroxime, cephalexin, loracarbef, ampicillin, amoxicillin clavulanate, bacampicillin, cloxicillin, penicillin VK, ciprofloxacin, grepafloxacin, levofloxacin, lomefloxacin, norfloxacin, ofloxacin, sparfloxacin, trovafloxacin, azithromycin, and rythromycin. The bacteria, antifungal compound(s), and immunosuppressive compound(s) are administered concurrently or sequentially.
The invention also provides a method of reducing a symptom of an autoimmune disorder by identifying a patient suffering from or at risk of developing an autoimmune disorder, and administering to the patient a composition including Bacillus coagulans bacteria. The autoimmune disorder is psoriasis, Crohn's Disease, colitis, lupus, arthritis, or any other disorder that is characterized by a pathological increase in activation of immune cells (e.g., T cells) associated with a pathogenic agent (such as a bacteria, fungus or virus).
The invention further provides a method for decreasing a symptom of an autoimmune disorder in a mammal affected thereby, by administering to a mammal a composition that includes Bacillus coagulans bacteria. A symptom (e.g., scaling, blistering, skin lesions, itchiness, and/or pain) of the autoimmune disorder is decreased following the administration, compared to the severity of the symptom prior to the administration.
The invention also provides a method for decreasing serum TNF-α or other cytokine levels in a mammal that has been diagnosed with an elevated level of TNF-α, or one or more other cytokines. Normal human serum levels of TNFα range from undetectable to about 40 pg/ml of serum, with average values in the range of 3-10 pg/ml. TNF-α is preferably detected by, e.g., ELISA or other quantitative detection means. (Human TNF-α ELISA kit, Abazyme, Needham, Mass., or Millenia Diagnostic Product, Los Angeles, Calif.).
Serum cytokine levels (such as TNF-α levels) are decreased following the administration of Bacillus coagulans , when compared to serum cytokine (such as TNF-α) levels in the mammal prior to the administration. Elevated human serum levels (e.g., greater than about 40, 50, 60, 75, 85, 100, 125, 150, 200, 250, 300, or more pg/ml) prior to administration are associated with autoimmune disorders, and are reduced following a course of administration of Bacillus coagulans . A reduction in TNF-α levels confers a clinical benefit to the treated subject, e.g., a reduction in a symptom of an autoimmune disorder. The decrease is any measurable decrease, such as a decrease greater than about 1%, 5%, 10%, 15%, 25%, 50%, 60%, 75%, 85%, 90%, 95%, 99%, 99.9%, 99.99% or greater. The Bacillus coagulans bacteria are provided at a concentration of from about 1×10 8 to about 1×10 10 viable bacteria, such as 5×10 8 , 8×10 8 , 1×10 9 , or 5×10 9 viable bacteria.
The invention further provides a composition that includes a Bacillus coagulans bacterium, and an immunosuppressive agent. The composition is in the form of a capsule, tablet, powder, or liquid. The Bacillus coagulans bacteria can be Bacillus coagulans hammer or derived from Bacillus coagulans hammer, e.g., Bacillus coagulans hammer strain Accession No. ATCC 31284.
The invention also provides a system containing medical food for the management of psoriasis or other disorder that includes Bacillus coagulans bacteria, where the medical food is formulated to provide at least about 1×10 6 viable Bacillus coagulans bacteria in the gastrointestinal tract of a mammal per day, based on a serving size of about 1 gram to about 2 grams of the medical food taken up to about twice a day, and instructions for use thereof. In embodiments of the invention, the medical food optionally includes a non-microbially derived anti-fungal agent, an immunosuppressive agent, or a non-microbially derived anti-fungal agent and an immunosuppressive agent.
Other features and advantages of the invention will be apparent from the following detailed description and from the claims.
DETAILED DESCRIPTION
The mammalian gastrointestinal tract is a complex ecosystem host to a diverse and highly evolved microbial community composed of hundreds of different microbial species. A perturbation of the interactions that occur between this complex microbial community and the mammal can lead to diseases such as illnesses associated with deficient or compromised microflora (e.g., gastrointestinal tract infections, inflammatory bowel diseases (such as Crohn's disease and ulcerative colitis), irritable bowel syndrome, antibiotic-induced diarrhea, constipation, food allergies, cardiovascular disease, psoriasis, and certain cancers. “Functional food,” e.g., those that contain beneficial bacteria such as Bacillus coagulans are useful as therapies to prevent autoimmune diseases and other diseases characterized by an increase in TNF-α compared to normal, control levels.
Lactic acid bacteria (LAB) display numerous health benefits beyond providing general digestive value. They cooperatively maintain a physiological balance between the gastrointestinal tract and immune system. When this balance is disrupted, disease and inflammation often result. Deleterious bacteria are competitively inhibited by the mucosal adherence or transient colonization of beneficial microflora such as Bacillus coagulans . A healthy gastrointestinal tract with adequate mucus production and appropriate bacterial colonization prevents or inhibits the growth of pathogenic or opportunistic microorganisms, modulates disease processes, and prevents widespread inflammatory disorders.
Bacillus coagulans is an L+ lactic acid-producing bacterium that has been shown to be highly effective in the colonization of the various mucosal surfaces of the gastrointestinal tract. Unlike strictly vegetative species of lactic acid bacteria (e.g., Lactobacillus, Bifidobacterium , and other bacteria) that are used in therapeutic applications, Bacillus coagulans survives intact after exposure to extremely low pH of stomach and bile acids. This is accomplished due to the extremophile nature of the vegetative form of this organism (thermo-tolerant, acidophilic, baro-tolerant, and halo-tolerant), and that it forms endospores. In addition, Bacillus coagulans is highly competitive, which is an important feature for the high-density colonization that is required to promote physiological changes in the small and large bowel. Further, Bacillus coagulans has been shown in Minimum Inhibitory Concentration (MIC) dilution (in vitro) studies to inhibit many enteric bacterial pathogens ( Escherichia, Proteus, Clostridium, Campylobacter, Shigella, Salmonella, Enterococcus, Staphylococcus, Streptococcus , and others), which require a higher than neutral pH in order to proliferate. MIC studies have also been performed that indicate high inhibitory activity on various mycotic pathogens challenged with Bacillus coagulans.
The methods and compositions of the present invention are useful in the treatment of autoimmune diseases. Autoimmune diseases can affect almost any organ or tissue of the body, and are thus amenable to classification by the affected tissue(s). It is recognized that an autoimmune disease or disorder can impact one or more tissues. Autoimmune disorders that affect the blood or vasculature including autoimmune hemolytic anemia, pernicious anemia, polyarteritis nodosa, systemic lupus erythematosus, and Wegener's granulomatosis. Autoimmune disorders of the gastrointestinal system include autoimmune hepatitis, Behçet's disease, Crohn's disease, primary biliary cirrhosis, scleroderma, ulcerative colitis, and Irritable Bowel Syndrome (IBS). Autoimmune disorders that affect the ocular system include Sjögren's syndrome, type 1 diabetes mellitus, and uveitis. Autoimmune disorders that affect the endocrine system include Graves' disease, and thyroiditis. Autoimmune disorders that affect the cardiovascular system include myocarditis, rheumatic fever, scleroderma, and systemic lupus erythematosus. Autoimmune disorders that affect connective tissue include ankylosing spondylitis, rheumatoid and reactive arthritis, and systemic lupus erythematosus. An autoimmune disorder that affects the kidneys is glomerulonephritis. An autoimmune disorder that affects the lungs is glomerulonephritis is sarcoidosis. Autoimmune disorders that affect the musculoskeletal system include dermatomyositis, myasthenia gravis, polymyositis, and fibromialgia. Autoimmune disorders that affect the neurological system include Guillain-Barré syndrome, and multiple sclerosis. Autoimmune disorders that affect the skin include alopecia areata, pemphigus (also termed pemphigoids), psoriasis, and vitiligo.
Symptoms of autoimmune disease include fatigue, dizziness, malaise, fever, and decreased platelet and/or eosinophil counts. Further, certain autoimmune diseases are characterized by destruction of a type of tissue (e.g., destruction of islet cells of the pancreas in diabetes) or the increase in organ size (e.g., thyroid enlargement in Graves Disease). For treatment or prevention of such diseases or conditions and reduction of symptoms associated with these conditions, compositions that contain Bacillus coagulans bacteria are administered according to the methods described herein.
TNF-α is a naturally occurring cytokine, which is produced by activated immune cells. However, excessive activation of immune effector cells and overproduction of TNF-α can cause severe inflammation and tissue damage. TNF-α plays a major role in a number of disease states, e.g., psoriasis, Crohn's disease, rheumatoid arthritis, ulcerative colitis, and ankylosing spondylitis. Reducing the level of TNF-α in patients suffering from or at risk of developing autoimmune disease or inflammatory disease states alleviates symptoms of the disease and prevents or slows disease progression.
Reducing TNF-α by administering Bacillus coagulans confers a clinical benefit (e.g., reduced inflammation) with little or none of the side effects associated with other, non-microbial TNF-α inhibitors (e.g., infliximab, etanercept, and adalimumab). Administration of Bacillus coagulans confers a clinical benefit to subjects identified as suffering from or at risk of developing the following exemplary autoimmune disorders.
Psoriasis
Psoriasis is a skin disease that is characterized in part by abnormal proliferation and differentiation of keratinocytes, T-cell and endothelial cell activation, local vascular changes, and neutrophil accumulation as well as other immunological processes, e.g., altered levels of cytokines. Results of cyclosporine and fluconazole treatments also demonstrate that bacterial and mycotic agents play a significant role in psoriasis.
Psoriasis generally results from a genetic defect in combination with external triggers that affect the features of the disease. The cellular immune system plays a dominant role in exacerbation of psoriasis. Microorganisms such as β-hemolytic streptococci, Staphylococcus aureus and Candida albicans are external triggers that release factors which serve as superantigens, and stimulate the T cells to initiate psoriasis, which often resulting in a “pathogenic circle” of repeated incidences of the disease. The source of the microorganisms may be in the skin itself or in distal locations, such as Streptococcus in the throat or Candida albicans in the gut. From these locations, the microorganisms cause the release of superantigens that travel through the host's vascular system to reach the skin and initiate the psoriatic process.
There are many different forms of psoriasis, including plaque psoriasis (vulgaris psoriasis), guttate psoriasis, pustular psoriasis, erythrodermic psoriasis, nail psoriasis, scalp psoriasis, inverse psoriasis, and psoriatic arthritis. Symptoms of psoriasis vary among the forms of psoriasis, and between affected individuals. As used herein, a “symptom” of psoriasis includes any observable, measurable or detectable sign or indication of any form of psoriasis or a psoriasis-related condition. A patient suffering from psoriasis has one or more symptoms of psoriasis. Psoriasis symptoms include scaling, blistering, skin lesions, itchiness, and joint pain. Other symptoms of psoriasis are known to those of ordinary skill in the art. Psoriasis is diagnosed by the observation or detection of one or more symptoms of psoriasis. Generally, a patient suffering from or at risk of developing psoriasis has one or more symptoms of psoriasis, or a family member having psoriasis or a symptom of psoriasis.
Indications of treatment of psoriasis include any detectable change (e.g., a decrease or disappearance) in a symptom of psoriasis, as measured by size, severity, duration, or the presence or absence of relapses of affected skin. A preferred method of determining the efficacy of a treatment is the measurement of the change in the total psoriatic lesion area following Bacillus coagulans treatment, as compared to the in total psoriatic lesion area prior to treatment. Also, a measurable decrease in the amount of serum TNF-α in a patient undergoing psoriasis treatment indicates the efficacy of the treatment. Further, the efficacy of treatment can be determined by the decrease in pathogenic microorganisms present in the gastrointestinal tract of the patient undergoing treatment, such as by measuring the presence of these microorganisms in stool measurement in stool or other biological materials.
Inflammatory Bowel Disease
Human inflammatory bowel disease (IBD) is a group of intestinal inflammatory diseases that can be subdivided in ulcerative colitis (UC) and Crohn's disease (CD) based on typical clinical manifestations. The symptoms of both are extremely unpleasant and impact all aspects of quality of life. They include diarrhea, abdominal pain, rectal bleeding, fever, nausea, weight loss, lethargy and loss of appetite. If left untreated, malnutrition, dehydration and anemia follow, which, in extreme cases, lead to death. Although UC and CD show a considerable degree of similarity in etiology and epidemiology, they are entirely different in pathology. UC is restricted to the colon. CD, however, has been observed throughout the entire intestinal tract, from the mouth to the rectum. Inflammation is restricted to the mucosa in UC, whereas in CD the inflammation can be transmural, i.e., penetrating the bowel wall. This often leads to the development of perianal fistulae. An imbalance in T-helper (Th) subsets of T cells, so called Th1 and Th2, differentiates CD from UC on an immunological basis. In UC, an over-expression of Th2 type cytokines (IL-4, IL-5) has been demonstrated, whereas in CD, Th1 type cytokines (IL-12, IFN-γ) predominate.
CD and UC involve an interaction between genetic and environmental factors, such as bacterial agents. Abnormal immune responses, driven by the intestinal microflora, occur in IBD. Most experimental models for IBD cannot be established in germ-free animals. In one art-recognized experimental model, IL-10−/− mice show that the appearance of mucosal adherent colonic bacteria is causative of the development and maintenance of the inflammation.
Breach of tolerance towards normal intestinal microflora may thus be the driving force behind IBD. The absence of tolerance to the indigenous microflora also appears in trinitrobenzene sulphonic acid (TNBS)-induced colitis. The administration of IL-10, a central mediator in down-regulation of immune reactions, restores healthy status by reestablishing tolerance. This treatment does not, however, affect immune reactivity towards heterologous bacterial antigen. Staphylococcal enterotoxin B can abrogate self-tolerance at the intestinal epithelium. IL-10 can counteract this by preventing the activation of T cells that contribute to epithelial cell damage. T-cell clones stimulated by indigenous aerobic flora and bifidobacteria were also identified in patients with IBD.
Higher bacterial load has been reported in the mucus of IBD patients. Although a number of reports measure no significant differences in the flora composition of UC patients when compared with controls, two recent studies indicate significant decrease of lactobacilli in UC. There are conflicting reports on the composition of the microflora in CD although it is difficult to compare disease stages when assessed in different centers. Bifidobacterium species are found to be decreased in CD. A significant increase in Escherichia coli and Bacteroides fragilis was detected in the ileum and of E. coli and lactobacilli in the colon, although lactobacilli , together with bifidobacterial scores, have also been found significantly reduced in CD patients.
The development of IBD is in some cases linked to viral or bacterial infection ( Mycobacteria, Shigella, Salmonella, Yersinia, Clostridium difficile, Bacteroides vulgatus ) but to date no etiological agent has been identified for IBD. Recently, however, a DNA sequence has been identified in lamina propria mononuclear cells of which the presence and serum reactivity towards the according peptide highly correlates with CD. This presently unknown sequence is not of human origin and shows homology with bacterial tetR/acrR transcription regulators.
Systemnic Lupus Erythematosus (SLE)
An inflammation of the connective tissues, SLE impacts one or more organs or tissues in a subject. It is up to nine times more common in women than men. Further, SLE impacts black women three times as often as Caucasian women. The condition is aggravated by sunlight. Symptoms include fever, weight loss, hair loss, mouth and nose sores, malaise, fatigue, seizures and symptoms of mental illness. Identification of a patient suffering SLE from is accomplished by identifying one or more of these symptoms in the patient. Ninety percent of patients experience joint inflammation similar to rheumatoid arthritis. Fifty percent develop a classic “butterfly” rash on the nose and cheeks. Raynaud's phenomenon (extreme sensitivity to cold in the hands and feet) appears in about 20 percent of people with SLE. Current treatments are limited to the use of anti-inflammatory drugs to control arthritis symptoms, and topical steroidal creams to treat skin lesions, while oral steroids, such as prednisone, are used for the systemic symptoms. One or more symptoms of SLE are reduced following treatment with Bacillus coagulans bacteria.
Rheumatoid Arthritis
Rheumatoid arthritis is a systemic disorder in which immune cells attack and inflame the membrane around joints. It also can affect the heart, lungs, and eyes. Of the estimated 2.1 million Americans with rheumatoid arthritis, approximately 1.5 million (71 percent) are women. Symptoms of the disease include inflamed and/or deformed joints, loss of strength, swelling, and pain. Identification of a patient suffering from rheumatoid arthritis is accomplished by identifying one or more of these symptoms in the patient. Current treatment modalities include rest and anti-inflammatory drugs. One or more symptoms of rheumatoid arthritis are reduced following treatment with Bacillus coagulans bacteria.
Scleroderma (Systemic Sclerosis)
Scleroderma involves the hyperactivity of certain immune cells, which produce fibrous, scar-like tissue in the skin, internal organs, and small blood vessels. It affects women three times more often than men overall, but increases to a rate 15 times greater for women during childbearing years, and appears to be more common among black women than Caucasian women. Symptoms of scleroderma include the appearance of Raynaud's phenomenon, as well as swelling and puffiness of the fingers or hands. Often, skin thickening follows, and other symptoms include skin ulcers on the fingers, joint stiffness in the hands, pain, sore throat, and diarrhea. Identification of a patient suffering from scleroderma is accomplished by identifying one or more of these symptoms in the patient. Current treatments of scleroderma include D-penicillamine, which has been shown to decrease skin thickening. This disorder also impacts other organs such as the kidneys, esophagus, intestines, and blood vessels and thus requires multi-system treatments. One or more symptoms of scleroderma are reduced following treatment with Bacillus coagulans bacteria.
Sjogren's Syndrome
Sjögren's syndrome (also called Sjögren's disease) is a chronic, slowly progressing inability to secrete saliva or tears. It can occur alone or with rheumatoid arthritis, scleroderma, or systemic lupus erythematosus. Nine out of 10 cases occur in women, most often at or around mid-life. Symptoms of this disorder include dryness of the eyes and mouth, swollen neck glands, difficulty swallowing or talking, unusual tastes or smells, thirst, tongue ulcers, or severe dental caries. Identification of a patient suffering from Sjögren's syndrome is accomplished by identifying one or more of these symptoms in the patient. Current treatments include interventions to keep the mouth and eyes moist (including drinking a lot of fluids and using eye drops, as well as good oral hygiene and eye care). One or more symptoms of Sjögren's syndrome are reduced following treatment with Bacillus coagulans bacteria.
Multiple Sclerosis (MS)
Multiple sclerosis is a disease of the central nervous system that usually first appears between the ages of 20 and 40; it affects women twice as often as men. MS is the leading cause of disability among young adults. MS is recognized to be an unpredictable disease of the central nervous system, and can range from relatively benign to somewhat disabling to devastating, as communication between the brain and other parts of the body is disrupted. Symptoms of MS include fatigue, problems walking, bowel and/or bladder disturbances, visual problems, changes in cognitive function, including problems with memory, attention, and problem-solving, abnormal sensations such as numbness or “pins and needles,” changes in sexual function, pain, depression and/or mood swings, tremor, speech and swallowing problems, and impaired hearing. Identification of a patient suffering from multiple sclerosis is accomplished by identifying one or more of these symptoms in the patient. The vast majority of patients are mildly affected, but in the worst cases MS can render a person unable to write, speak, or walk. One or more symptoms of MS are reduced following treatment with Bacillus coagulans bacteria.
Myasthenia Gravis
Myasthenia gravis is a chronic autoimmune disorder characterized by gradual muscle weakness, often appearing first in the subject's face and often characterized by drooping eyelids, as well as double vision, difficulty breathing, talking, chewing, and swallowing. Identification of a patient suffering from myasthenia gravis is accomplished by identifying one or more of these symptoms in the patient. The drug edrophonium is currently used as a treatment, along with daily rest periods, which can improve muscle strength. One or more symptoms of myasthenia gravis are reduced following treatment with Bacillus coagulans bacteria.
Guillain-Barre Syndrome
Guillain-Barré syndrome is a disorder in which the body's immune system attacks part of the peripheral nervous system. The first symptoms of this disorder include varying degrees of weakness or tingling sensations in the legs. Identification of a patient suffering from Guillain-Barré syndrome is accomplished by identifying one or more of these symptoms in the patient. In many instances, the weakness and abnormal sensations spread to the arms and upper body. These symptoms can increase in intensity until the muscles cannot be used at all and the patient is almost totally paralyzed. In these cases, the disorder is life threatening and is considered a medical emergency. The patient is often put on a respirator to assist with breathing. Most patients, however, recover from even the most severe cases of Guillain-Barré syndrome, although some continue to have some degree of weakness. Guillain-Barré syndrome is rare. Usually Guillain-Barré occurs a few days or weeks after the patient has had symptoms of a respiratory or gastrointestinal viral infection. Occasionally, surgery or vaccinations will trigger the syndrome. The disorder can develop over the course of hours or days, or it may take up to 3 to 4 weeks. Because the signals traveling along the nerve are slower, a nerve conduction velocity (NCV) test is used to aid diagnosis. Increased protein in the cerebrospinal fluid is also used to diagnose Guillain-Barré syndrome. One or more symptoms of Guillain-Barré syndrome are reduced following treatment with Bacillus coagulans bacteria.
Hashimoto's Thryroiditis
Hashimoto's thyroiditis is a type of autoimmune disease in which the immune system destroys the thyroid, the gland that helps set the rate of metabolism. It attacks women 50 times more often than men. Symptoms of this disorder include low levels of thyroid hormone, resulting in mental and physical slowing, greater sensitivity to cold, weight gain, coarsening of the skin, and goiter (a swelling of the neck due to an enlarged thyroid gland). Identification of a patient suffering from Hashimoto's thyroiditis is accomplished by identifying one or more of these symptoms in the patient. Currently, thyroid hormone replacement therapy is used to treat this disorder. One or more symptoms of Hashimoto's thyroiditis are reduced following treatment with Bacillus coagulans bacteria.
Graves' Disease
Graves' disease is one of the most common autoimmune diseases, and impacts women about seven times as often as men. Subjects with Graves' disease produce an excessive amount of thyroid hormone. Symptoms of Graves' disease include weight loss due to increased energy expenditure, increased appetite, heart rate, and blood pressure, tremors, nervousness and sweating, as well as frequent bowel movements. Identification of a patient suffering from Graves' disease is accomplished by identifying one or more of these symptoms in the patient. Treatment options include anti-thyroid drug therapy or removal of the thyroid gland, e.g., surgically or by radioiodine treatment. One or more symptoms of Graves' disease are reduced following treatment with Bacillus coagulans bacteria.
Insulin-Dependent (Type 1) Diabetes
Type 1 diabetes is caused by too little insulin production in the pancreas, and usually occurs in children and young adults, but it can occur at any age. Symptoms include increased thirst, increased urination, weight loss, fatigue, nausea, vomiting, and frequent infections. Identification of a patient suffering from diabetes is accomplished by identifying one or more of these symptoms in the patient. Insulin treatment is the current treatment modality. One or more symptoms of diabetes are reduced following treatment with Bacillus coagulans bacteria.
Inflammatory Bowel Disease
Crohn's disease (also called ileitis or enteritis) causes inflammation in the small intestine. Crohn's disease usually occurs in the lower part of the small intestine, called the ileum, but it can affect any part of the digestive tract, from the mouth to the anus. The inflammation extends deep into the lining of the affected organ. The inflammation can cause pain and can make the intestines empty frequently, resulting in diarrhea. Identification of a patient suffering from Crohn's disease is accomplished by identifying one or more of these symptoms in the patient. Crohn's disease is one form of inflammatory bowel disease. Crohn's disease can be difficult to diagnose because its symptoms are similar to other intestinal disorders such as irritable bowel syndrome and to another type of IBD called ulcerative colitis. Ulcerative colitis causes inflammation and ulcers in the top layer of the lining of the large intestine. Crohn's disease affects men and women equally and seems to run in some families. About 20 percent of people with Crohn's disease have a blood relative with some form of IBD, most often a brother or sister and sometimes a parent or child. One or more symptoms of Crohn's disease are reduced following treatment with Bacillus coagulans bacteria.
Ulcerative Colitis
Ulcerative colitis is a disease that causes inflammation and sores, called ulcers, in the lining of the large intestine. The inflammation usually occurs in the rectum and lower part of the colon, but it may affect the entire colon. Ulcerative colitis rarely affects the small intestine except for the end section, called the terminal ileum. Ulcerative colitis may also be called colitis or proctitis. Symptoms of UC include fatigue, weight loss, loss of appetite, rectal bleeding and loss of body fluids and nutrients. Identification of a patient suffering from UC is accomplished by identifying one or more of these symptoms in the patient. The inflammation makes the colon empty frequently, causing diarrhea. Ulcers form in places where the inflammation has killed the cells lining the colon; the ulcers bleed and produce pus. Crohn's disease differs from ulcerative colitis because it causes inflammation deeper within the intestinal wall. Also, Crohn's disease usually occurs in the small intestine, although it can also occur in the mouth, esophagus, stomach, duodenum, large intestine, appendix, and anus. Ulcerative colitis may occur in people of any age, but most often it starts between ages 15 and 30, or less frequently between ages 50 and 70. Children and adolescents sometimes develop the disease. Ulcerative colitis affects men and women equally and appears to run in some families. One or more symptoms of UC are reduced following treatment with Bacillus coagulans bacteria.
Celiac Disease
Celiac disease is a digestive disease that damages the small intestine and interferes with absorption of nutrients from food. Subjects with celiac disease cannot tolerate a protein called gluten, which is found in wheat, rye, and barley. When people with celiac disease eat foods containing gluten, their immune system responds by damaging the small intestine. Specifically, the intestinal villi are lost, resulting in malnutrition. Symptoms of Celiac disease include diarrhea, abdominal pain and bloating, gas, irritability, depression, weight loss, delayed growth, failure to thrive in infants, anemia, and fatigue. Identification of a patient suffering from Celiac disease is accomplished by identifying one or more of these symptoms in the patient. Celiac disease is also known as celiac sprue, nontropical sprue, and gluten-sensitive enteropathy. Celiac disease may be induced following surgery, pregnancy, childbirth, viral infection, or severe emotional stress. One or more symptoms of Celiac disease are reduced following treatment with Bacillus coagulans bacteria.
Vasculitis Syndromes
This is a broad and heterogeneous group of diseases characterized by symptoms including inflammation and damage to the blood vessels, thought to be brought on by an autoimmune response. Identification of a patient suffering from vasculitis is accomplished by identifying one or more of these symptoms in the patient. Any type, size, and location of blood vessel may be involved. Vasculitis may occur alone or in combination with other diseases, and may be confined to one organ or involve several organ systems. One or more symptoms of vasculitis are reduced following treatment with Bacillus coagulans bacteria.
Hematologic Autoimmune Diseases
Blood also can be affected by an autoimmune disorder. In autoimmune hemolytic anemia, red blood cells are prematurely destroyed by antibodies. Other autoimmune diseases of the blood include autoimmune thrombocytopenic purpura and autoimmune neutropenia. One or more symptoms of these blood disorders are reduced following treatment with Bacillus coagulans bacteria.
The present inventors recognize that certain autoimmune disorders affect primarily women, as noted for several autoimmune disorders described above. The present invention discloses the prevention or treatment of an autoimmune disorder in a female subject. In embodiments of the invention, the autoimmune disorder to be treated or prevented in a female patient is Hashimoto's disease (also known as hypothyroiditis), systemic lupus erythematosus, Sjogren's syndrome, antiphospholipid syndrome, primary biliary cirrhosis, mixed connective tissue disease, chronic active hepatitis, Graves' disease (also termed hyperthyroiditis), rheumatoid arthritis, scleroderma, myasthenia gravis, multiple sclerosis, or chronic idiopathic thrombocytopenic purpura.
Bacillus coagulans Therapy Reduces Gastrointestinal Infection by Autoimmune Disease-Associated Pathogenic Microorganisms
Many species of bacterial, mycotic and yeast pathogens possess the ability to cause a variety of disorders, including autoimmune disorders. Bacillus coagulans , a probiotic microorganism is useful in the prophylactic or therapeutic treatment of autoimmune conditions such as psoriasis, which are associated with infection by these aforementioned pathogens. Generally, Bacillus coagulans bacteria (i) possess the ability to produce and excrete enzymes useful in digestion (e.g., lactase, various proteases, lipases and amylases); (ii) demonstrate beneficial function within the gastrointestinal tract; (iii) serve to down-regulate the cytokine response as a result of bacterial/fungal/or mycotic interaction with the various mucosal cells; and (vi) are non-pathogenic. Bacillus coagulans bacteria are able to inhibit pathogenic yeast and other fungi, including Candida albicans, Candida tropicalis and Trichophyton mentagrophytes, Trichophyton interdigitale, Trichophyton rubrum , and Trichophyton yaoundei. Bacillus coagulans bacteria are also able to inhibit pathogenic bacteria, including Staphylococcus species, Streptococcuspyogenes species, Pseudomonas species, Escherichia coli, Clostridium species, Gardnereia vaginailis, Proponbacterium acnes, Aeromonas species, Aspergillus species; Proteus species; and Klebsiella species.
Strains of Bacillus coagulans bacteria are available from the American Type Culture Collection (ATCC), including the following accession numbers: Bacillus coagulans Hammer NRS 727 (ATCC No. 11014); Bacillus coagulans Hammer strain C (ATCC No. 11369); Bacillus coagulans Hammer (ATCC No. 31284); Bacillus coagulans Hammer NCA 4259 (ATCC No. 15949); and strains deposited under ATCC Accession Numbers 8038, 35670, 23498, 51232, 12245, 10545 and 7050. Purified Bacillus coagulans bacteria are also available from the Deutsche Sarumlung von Mikroorganismen und Zellkuturen GmbH (Braunschweig, Germany) using the following accession numbers: Bacillus coagulans Hammer 1915 (DSM No. 2356); Bacillus coagulans Hammer 1915 (DSM No. 2383, corresponds to ATCC No. 11014); Bacillus coagulans Hammer (DSM No. 2384, corresponds to ATCC No. 11369); and Bacillus coagulans Hammer (DSM No. 2385, corresponds to ATCC No. 15949). Bacillus coagulans bacteria can also be obtained from commercial suppliers such as K. K. Fermentation (Kyoto, Japan) and Nebraska Cultures (Walnut Creek, Calif.).
The Bacillus coagulans bacterial strain used to reduce infection by microbial pathogens is Bacillus coagulans hammer, or a strain derived therefrom. For example, the Bacillus coagulans bacterial strain is ATCC 31284, or a strain derived therefrom. These strains include, e.g., ATCC Numbers GBI-20, ATCC Designation Number PTA-6085, available to the public via the ATCC; GBI-30, ATCC Designation Number PTA-6086, available to the public via the ATCC; and GBI-40, ATCC Designation Number PTA-6087, available to the public via the ATCC; see U.S. Pat. No. 6,849,256 to Farmer, the contents of which are incorporated by reference in their entirety.
A composition comprising Bacillus coagulans bacteria in a pharmaceutically acceptable carrier suitable for oral administration to the gastrointestinal tract of a mammal (e.g., a human) animal is disclosed. Bacillus coagulans bacteria are provided in amounts sufficient to colonize the gastrointestinal tract of a mammal. The invention provides Bacillus coagulans bacteria at a concentration of from about 1×10 4 to about 1×10 12 viable bacteria, specifically about 1×10 6 to about 1×10 11 , more specifically about 1×10 8 to about 1×10 10 , and most specifically about 8×10 8 . Bacillus coagulans bacteria are provided as vegetative cells, spores, or a combination thereof.
Vegetative cells are formulated in a composition that protects the cells from being killed by the acid environment of the stomach. Cells formulated in this manner successfully traverse the stomach to colonize the small and/or large intestine. Accordingly, the invention includes a composition containing a Bacillus coagulans bacterium in a pharmaceutically acceptable acid-resistant (“enteric”) carrier. By acid-resistant is meant that the carrier or coating does not dissolve in an acidic environment. An acidic environment is characterized by a pH of less than 7. The acid-resistant carrier is resistant to acids at pH less than about 4.0. Preferably, the carrier does not dissolve in pH 2-3. Most preferably, it does not dissolve in pH of less than 2. To protect vegetative bacterial cells from stomach acids, the cells are coated or encapsulated with the acid-resistant carrier. The composition optionally includes other components such as glucose and phosphoric acid or other nutrient compounds to increase bacterial growth after removal of the carrier or coating. The invention also includes Bacillus coagulans bacteria in the form of spores, which are selected for the capability of germinating in the presence of bile acids such as cholic, deoxycholic and tauro-deoxycholic acids. Enterically coated and bile acid-resistant Bacillus coagulans bacteria are described in U.S. Ser. No. 10/287,904, filed Nov. 5, 2002, the contents of which are incorporated by reference in their entirety.
The compositions contain Bacillus coagulans bacteria and one or more biologically active compounds; such as a natural or synthetic compound that decreases or relieves a symptom of psoriasis. Exemplary compounds include immunosuppressants including methotrexate, cyclosporine, hydroxyurea, mycophenolate mofetil, sulfasalazine, 6-thioguanine, and other compounds such as retinoids.
Example 1
Preparation of Bacillus coagulans Bacteria
I. Preparation of Vegetative Bacillus coagulans
Bacillus coagulans is aerobic and facultative, and is typically cultured at pH 5.7 to 6.8, in a nutrient broth containing up to 2% (by wt) NaCl, although neither NaCl, nor KCl are required for growth. A pH of about 4.0 to about 7.5 is optimum for initiation of sporulation (i.e., the formation of spores). The bacteria are optimally grown at 20° C. to 45° C., and the spores can withstand pasteurization. Additionally, the bacteria exhibit facultative and heterotrophic growth by utilizing a nitrate or sulfate source. Bacillus coagulans strains and their growth requirements have been described previously (see e.g., Baker, D. et al, 1960. Can. J Microbiol. 6: 557-563; Nakamura, H. et al, 1988. Int. J. Syst. Bacteriol. 38: 63-73. In addition, various strains of Bacillus coagulans can also be isolated from natural sources (e.g., heat-treated soil samples) using well-known procedures (see e.g., Bergey's Manual of Systemic Bacteriology, Vol. 2, p. 1117, Sneath, P. H. A. et al., eds. Williams & Wilkins, Baltimore, Md., 1986).
Bacillus coagulans bacteria are cultured in a variety of media, although it has been demonstrated that certain growth conditions are more efficacious at producing a culture that yields a high level of sporulation. For example, sporulation enhanced by supplementing the culture medium with 10 mg/l of MgSO 4 sulfate, yielding a ratio of spores to vegetative cells of approximately 80:20. In addition, certain culture conditions produce a bacterial spore that contains a spectrum of metabolic enzymes particularly suited for the present invention (i.e., production of lactic acid and enzymes for the enhanced probiotic activity and biodegradation). Although the spores produced by these aforementioned culture conditions are preferred, various other compatible culture conditions that produce viable Bacillus coagulans spores are utilized in the practice of the present invention.
Suitable media for the culture of Bacillus coagulans include: TSB (Tryptic Soy Broth), GYE (Glucose Yeast Extract Broth), and NB (nutrient broth), which are all well known within the field and available from a variety of sources. Media supplements which contain enzymatic digests of poultry and/or fish tissue, and containing food yeast are particularly preferred. A preferred supplement produces a media containing at least 60% protein, and about 20% complex carbohydrates and 6% lipids. Media can be obtained from a variety of commercial sources, notably DIFCO (Newark, N.J.); BBL (Cockeyesville, Md.); and Troy Biologicals (Troy, Md.)
II. Preparation of Bacillus coagulans Spores
A culture of dried Bacillus coagulans Hammer bacteria (ATCC No. 31284) spores was prepared as follows. Approximately 1×10 7 spores were inoculated into one liter of culture medium containing: 30 g (wt./vol.) Tryptic Soy Broth; 10 g of an enzymatic-digest of poultry and fish tissue; and 10 g MnSO 4 . The culture was maintained for 72 hours under a high oxygen environment at 37° C. so as to produce a culture having approximately 6×10 9 cells/gram of culture. The culture was then centrifuged to remove the liquid culture medium and the resulting bacterial paste was re-suspended in 100 ml of sterile water and 20% malto-dextrin and lyophilized. The lyophilized bacteria were ground to a fine powder by use of standard good manufacturing practice (GMP) methodologies.
Example 2
Formulations and Administration
Vegetative bacterial cells and spores are administered at a dose of 10,000−10 11 cells per administration. A typical therapeutic composition of the present invention contains in a one-gram dosage formulation, from approximately 1×10 3 to 1×10 12 , and preferably approximately 2×10 5 to 2×10 10 , colony-forming units (CFU) of viable Bacillus bacteria (i.e., vegetative bacteria) or bacterial spores. Typically, Bacillus coagulans bacteria remain in and colonize the colon for a period of 3-5 days post-administration.
Formulation #1
Bacillus coagulans
8.0 × 10 8
(53 mg)
Saccharomyces boulardii
1.5 × 10 8
(7.5 mg)
Copper Sulfate
5
mcg
Vitamin C
50
mg
Selenium
2.5
mcg
Micro-Crystalline Cellulose
132
mg
Total 250 mg
Formulation #2
Bacillus coagulans
8.0 × 10 8
(53 mg)
Saccharomyces boulardii
1.5 × 10 8
(7.5 mg)
L-Lysine
75
mg
Maltodextrin
35
mg
Blue lake #1 Dye
1
mg
Aspartame
2
mg
Compressible Sugars
173
mg
Total 350 mg
Formulation #3
Bacillus coagulans
1.5 × 10 9
(100 mg)
Maltodextrin
35
mg
Microcrystalline Cellulose
140
mg
Total 350 mg
Formulation #4
Bacillus coagulans
1.5 × 10 9
(100 mg)
Sarccharomyces boulardii
2.5 × 10 8
(12.5 mg)
L-Lysine
75
mg
Microcrystalline Cellulose
163
mg
Total 350 mg
Formulation #5
Bacillus coagulans
1.5 × 10 9
(100 mg)
L-Lysine
75
mg
Fluconazole 2%
150
mg
Filler
25
mg
Total 350 mg
The invention provides for the addition of other useful ingredients. Many individuals that suffer from immune disorders of this nature also have been shown to have vitamin and mineral deficiencies. Hence, addition of vitamin and mineral supplements is useful for the dietary management of these disorders.
Example 3
Use of Bacillus coagulans Bacteria in the Treatment and Clinical Remission of Chronic Psoriasis
Probiotic bacteria reduce the numbers of pathogens in the gut of humans and animals. In addition, Bacillus coagulans bacteria downregulate the body's cytokine response to toxins and pathogenic organisms.
A number of deleterious microorganisms promote over-stimulation of immune system. In the case of psoriasis, this leads to the production of cytokines (TNF-a) that cause the formation of dermal plates. Candida albicans is the underlying infection in these circumstances. It is common for physicians today to prescribe systemic antifungal compounds to reduce psoriatic lesions. Unfortunately, the antifungal most often used in these circumstances is Fluconazole, which can only be used for 30 days (as per FDA guidelines). With these issues in mind, studies were carried out to determine whether Bacillus coagulans lactic acid bacteria could be employed to reduce the number of Candida species in the stool while down regulating the production of TNF-a as a result of the Candida infection.
Twelve human patients with chronic psoriasis were studied at a General practice clinic in Cleveland, Ohio over a three-month period. Patients were provided with capsules containing Bacillus coagulans bacteria (7.5×10 8 colony forming units (CFU)) and microcrystalline cellulose as a carrier, and instructed to take two capsules per day. There were no restrictions on the time of day of consumption or if the two capsules were taken at the same or different times during the day. The treatment lasted three months; patients were observed at the beginning and end of the treatment.
Results after a two-month period indicated that Bacillus coagulans therapy was nearly 100% effective in reducing the surface area of psoriatic plates in patients suffering from Psoriasis vulgaris. The physician that conducted the study did not that a few younger patients (16-25 years of age) that had plates over >60% of their respective bodies did show results much quicker than the patients that were older (50 years of age or older), and had been affected by the disease for a much longer period (>20 years). Five patients that showed excellent results after therapy discontinued use of the formulation (for various reasons) and their psoriatic plates returned very quickly. After re-initiating therapy, the plates started to recede again. This indicates that the underlying Candida infection may not be totally eliminated and that a longer period of therapy may be required to maintain the results. Moreover, some individuals are more susceptible to mycotic infection and as a result, these individuals need to manage this state with continued use of the formulation. The usage parameters may be different for dietary management after initial results but, to guarantee that the initial results are maintained, the a minimum of one capsule a day ongoing may be sufficient.
Example 4
Use of Bacillus coagulans Bacteria to Reduce Serum TNF-α Levels
Colonization of the mammalian gastrointestinal tract by pathogenic microorganisms leads to the aberrant production of cytokines (e.g., TNF-α), which cause symptoms of psoriasis, such as dermal plates. Oral administration of Bacillus coagulans bacteria is examined for the ability to decrease cytokine production in human subjects suffering from or at risk of developing psoriasis.
Materials and Methods
Subjects are identified by the presence or past incidence of one or more symptoms of psoriasis, or by a family history of the disease (one or more parents, grandparents or siblings having one or more symptoms of psoriasis). Non-affected individuals are used as controls. Serum cytokine levels are determined prior to Bacillus coagulans bacteria treatment, at regular intervals throughout the duration of the treatment, and upon completion of the treatment. Measured cytokines include TNF-α and interleukin-6 (IL-6). Measurement of serum cytokine levels is performed by methods known in the art, such as ELISA. Bacillus coagulans bacteria are administered to affected and non-affected subjects such that at least about 1×10 6 viable Bacillus coagulans bacteria are delivered in the gastrointestinal tract of each subject per day. Treatments last at least about 10 days, e.g., about 10, 15, 20, 30, 45, 60, 75, 90 or 120 days.
Results
Human patients suffering from or at risk of developing psoriasis have higher levels of TNF-α than non-affected controls. Treatment with Bacillus coagulans bacteria results in a decrease in serum TNF-α levels in affected subjects.
Example 5
Medical Foods Containing Bacillus coagulans Bacteria
A “medical food” means a food which is formulated to be consumed or administered enterically under the supervision of a physician and which is intended for the specific dietary management of a disease or condition for which distinctive nutritional requirements, based on recognized scientific principles, are established by medical evaluation. (See, 21 USC 360ee(b)(3)). For subjects suffering from or at risk of developing an autoimmune disease, the compositions containing Bacillus coagulans bacteria are nutritionally complete formulas of medical foods. Alternatively, the compositions containing Bacillus coagulans bacteria are nutritionally incomplete formulas of medical foods.
Medical foods containing Bacillus coagulans bacteria are specially formulated and processed for subjects suffering from or at risk of developing an autoimmune disease, such as a subject who requires the medical as a major treatment modality. Typically, the medical foods containing Bacillus coagulans bacteria medical foods are formulated as an enteral nutrition product, i.e., it is provided through the gastrointestinal tract, taken by mouth, or provided through a tube or catheter that delivers nutrients beyond the oral cavity or directly to the stomach. The medical food is formulated to provide at least about 1×10 6 viable Bacillus coagulans bacteria in the gastrointestinal tract of a mammalian subject per day, based on a serving size of about 1 gram to about 2 grams of the medical food taken up to about twice a day. The medical food also optionally includes a non-microbially derived anti-fungal agent, an immunosuppressive agent, or a non-microbially derived anti-fungal agent and an immunosuppressive agent.
Subjects for whom medical foods containing Bacillus coagulans bacteria are appropriate are identified by the presence or past incidence of one or more symptoms of an autoimmune disease such as psoriasis, or by a family history of the disease (one or more parents, grandparents or siblings having one or more symptoms of an autoimmune disease).
Example 6
Use of Bacillus coagulans Bacteria in the Treatment of Other Autoimmune Disorders
Twelve human patients with Crohn's disease were studied at a general practice clinic in Cleveland, Ohio over a one-month period. Patients were provided with capsules containing Bacillus coagulans bacteria (1.5×10 9 colony forming units (CFU)) and microcrystalline cellulose as a carrier, and instructed to take one capsule per day. There were no restrictions on the time of day of consumption. The treatment lasted one month; patients were observed at the beginning and end of the treatment.
Results after one month indicated that all 11 out of 12 patients responded well to the formulation. One patient dropped out without explanation. The incidence of diarrhea was reduced by over 75% and abdominal pain and spasms were reduced significantly. Crohn's disease is diagnosed symptomatically; thus, a significant reduction in the number and severity of symptoms experienced each day is a notable improvement in individuals that suffer from this disease.
Other embodiments are within the following claims. | The present invention describes the use of lactic acid bacteria, particularly lactic acid producing members of the genus Bacillus , in treating digestive-related immune disorders by downregulating of cytokines and by inhibiting pathogenic or deleterious microorganisms in the gastrointestinal tract. Specific formulations of Bacillus coagulans for various immune disorders are elaborated. | 8 |
BACKGROUND OF THE INVENTION
The invention herein described was made in the course of or under a contract or subcontract thereunder, with the United States Navy.
The present invention relates generally to marine equipment handling systems and more particularly to such systems for lowering and retrieving bulky and heavy objects from ships and other unstable surface platforms.
In oceanographic work it often is necessary to deploy large and bulky objects from surface vessels for purposes of underwater exploration, observation or the like, and subsequently to retrieve the objects to, and sometimes into, the vessel from which deployed. For example, surveilance sonar systems may employ sonar transducer arrays which are very large in size and very substantial in weight, of the order of many thousands of pounds. Such arrays may conveniently be tethered by a single support line even to a relatively unstable surface platform such as a ship, during deployment and normal operation of the array at depth. During deployment the cable may be paid out sufficiently freely that even abrupt relative motion between the ship and array will not unduly load the cable, and when the array is at its operating depth which typically may be some thousands of feet, the inherent resilience of such long length of cable will permit heaving and other ship motion with respect to the array without excessive loading of the cable and without transmittal of sufficient force loading to the array as to cause it to attempt to follow the ship motion.
During retrieval of such arrays, however, several problems arise. As the array is hoisted upwardly into close proximity with the ship, the short length of cable remaining between the ship and array has too little resilience to permit any substantial relative motion between them, and the array accordingly is constrained to attempt to follow vertical motion of the ship. The resultant extreme fluctuations in loading on the cable may well exceed its strength, causing loss of the array. Also, if as is often the case the array is to be winched into engagement with the ship or into a well or hold formed within the ship, it is necessary that the array be placed into and held in proper orientation with respect to the ship at the moment of contact. Use of heavier cable can be of little if any help on this latter problem, of course, and is of limited benefit even with respect to the cable overload problem because generally cable strength can be improved only at the expense of cable weight, and where extremely long lengths of cable are required the cable weight itself may become the major part of the load and thus become the limiting factor.
SUMMARY OF THE INVENTION
The present invention has as its principal objective the provision of safe, reliable and relatively low cost systems for retrieval of submersible objects such as sonar arrays operating from an unstable surface platform. The system requires only passive devices to enable automatic location, positioning and alignment, latching and loading of the submersible object during retrieval operations, and provides the desired visibility to operators on shipboard indicating that capture and retrieval of the object is progressing in safe and orderly manner.
In the exemplary embodiment hereinafter particularly described, the submersible object is a large sonar array which is tethered to a surface ship by a single winch-operated main support line during the launch operation, during sonar operation at depth, and during retrieval back to a point approximately one or two hundred feet below the bottom of the ship. At this point, at which the ship's motion may begin to load the cable excessively, a retrieval or messenger device is lowered to the array by means of two cables paid out from the ship. The messenger cables are in line with the roll axis of the ship, and the messenger is centered with respect to the array cable by means of a centering device which engages and travels along the array main support line. The array and messenger are provided with cooperating ramp and follower elements which serve automatically to align the messenger and array angularly as they come vertically together, and the array and messenger also include cooperating latch elements which operate automatically upon attainment of the proper angular orientation of the messenger and array to lock them together. The combined load of the messenger and array then is taken up by the messenger cables, and the assemblage thus constituted is hauled upwardly to or into the ship. During this phase of the recovery the array main support line is unloaded either partially or completely as preferred.
BRIEF DESCRIPTION OF THE DRAWINGS
The foregoing and other objects, features and advantages of the invention will become more fully apparent and the invention be further understood by reference to the following detailed description when read in conjunction with the accompanying drawings, wherein:
FIG. 1 illustrates the marine handling system of the invention as applied to a ship-carried sonar array;
FIG. 2 is a side view, partially in section, illustrating the messenger device which forms part of the marine handling system of FIG. 1;
FIG. 3 is a top view, partially in section, of the messenger device;
FIGS. 4A and 4B are fragmentary views of latching elements which form part of the centering mechanism of the messenger device;
FIG. 5 is a fragmentary perspective of the cable stops which also form part of that centering mechanism; and
FIG. 6 is a fragmentary perspective of the latch trip mechanism of the messenger device of FIG. 2.
DESCRIPTION OF THE PREFERRED EMBODIMENT
As previously indicated, the marine equipment handling system of the present invention has application to a variety of oceanographic and other underwater equipments such as ocean bottom environmental capsules, drilling and sampling apparatus, sonars and the like. As illustrated in FIG. 1 the invention is shown applied to a surveillance sonar array the supporting framework for which is designated generally by reference numeral 11 in FIG. 1. The sonar transducers (not shown) would be mounted within this framework in suitably disposed array to form the desired sonar transmit or receive patterns. Typically an array assembly such as the one shown would be perhaps 30 to 50 feet in each of its face dimensions and 5 to 8 feet in depth, and weigh 25 to 50 tons when fully fitted with the transducer elements which it is to carry.
The array 11 is suspended by a single main support line 13 from a surface platform shown as a ship 15 having a hold or well 17 into which the array 11 may be drawn upon retrieval as hereinafter explained. In the particular system being described the operating depth for the array may be one or more miles, and the need for such extreme length of cable poses definite limits on the diameter and tensile strength of cable which can be used with a working load of this magnitude. Additionally, this main support line typically has incorporated within it a number of electrical conductors, often a relatively large number, providing power and signal transmission to and from the submerged array when operating at depth. The inclusion of such electrical conductors within the cable tends to make it more fragile and prone to failure through electrical discontinuity in addition to the possibility of mechanical breakage due to overstress.
These problems are most acute during retrieval of the submerged object, since during launch the cable normally is paid out at a sufficiently rapid rate that the submerged object does not heavily load it, and during operation at the working depth there is sufficient of the main support line out that the resilience inherent in such long cable length effectively decouples the ship's motion from the lower portions of the cable and limits the transients in loading of the upper portions. Depending upon the sea state, however, the ship's heave and other motions may impose loading on the cable far in excess of its load capacity as the array is retrieved and hauled upwardly into proximity with the ship. The short length of cable then outstanding constrains the array to attempt to follow ship's motion and the forces generated in the process may become far greater than the normal load capability of the cable. Additionally, if the array is to be retrieved through an opening in the ship's hull and raised into a well or hold within the ship, as shown, the array must of course be properly oriented with respect to such opening and a single cable however strong can not provide this necessary orientation.
In accordance with the invention, retrieval of the array may readily and reliably be accomplished by use of a messenger device designated generally by reference numeral 19 in FIG. 1, which is lowered from the ship 15 to intercept the array 11 when it reaches a point approximately one or two hundred feet below the ship. Messenger 19 engages the array at that point to properly orient it with respect to the ship and at the same time to relieve the main support line at least partially of its loading. The messenger device is carried by two cables 21 and 23 respectively connected adjacent its opposite ends, with the upper ends of these cables being connected to suitably synchronized winches (not shown) carried within the ship's structure.
While the details of the messenger device and of its cooperative relation with the array are best shown in FIGS. 2-6 and will be described in reference to those figures, it may be noted in FIG. 1 that the messenger comprises a centering mechanism designated generally by reference numeral 25 which serves to maintain the messenger and array in approximate lateral alignment as the two approach each other on retrival, complementary ramp and follower means designated generally by reference numerals 27-29 and mounted to the messenger and array, respectively, for bringing them into angular alignment during retrieval, and latching mechanisms 31 disposed at opposite ends of the messenger and engaging correspondingly positioned bail elements 33 on the array 11 for locking them together. The general arrangement is such that as the array 11 and messenger 19 are brought into interengagement, either by lowering the messenger toward the array or by raising the array toward the messenger, the messenger centering mechanism 25 operates to hold the messenger and array roughly centered with respect to each other in the lateral sense, and any angular misalignment of the messenger and array is corrected by operation of the ramp and follower elements 27 and 29.
Ramp element 27 is of circular section and includes two similarly sloped camming surfaces each of which extends through 180°, and the follower includes two rollers spaced apart by the diameter of the circle defined by the ramp element. As shown, the camming surfaces and rollers are so disposed that gravity acts to effect any rotation of the array about its vertical axis needed to bring it into alignment with the messenger. When such alignment is achieved the latch devices 31 and 33 operate automatically to interlock the messenger and array together for subsequent hoisting of the resultant assembly by the messenger cables 21 and 23.
Referring now to FIG. 2, the messenger 19 is shown to comprise a generally rectangular frame 35 from which depend two pairs of roller support brackets 37 each of which carries a roller support block 39 at its lower end. A shaft 41 having its opposite ends carried in the support blocks 39 of each bracket pair rotatably mounts a roller element 43, these rollers and their associated support blocks preferably being of the generally conical configuration shown to assist in operation of the centering mechanism next to be described.
As best seen in FIGS. 3-5, the centering mechanism 25 comprises four cables 45-48 each of which connects between a common centering ring 50 and one end of a tensioning spring the other end of which is connected to the messenger frame structure; one such spring is visible at 52 in FIG. 3 and the tubular housings for the others are indicated at 53-55. To enable the required distance of travel of these cables and springs within the available space, each of the cables preferably is provided with pulleys 57 to enable their being doubled back as shown. Each cable has fixed to it a pair of conical stops 59 (FIG. 5) spaced apart slightly so as to enable reception of a toggle member 61 between them. This toggle as best shown in FIGS. 4A and 4B comprises a crank shaped member pivotally mounted as at 63 to the messenger frame structure 35. Its shape is such that the toggle is urged by gravity to rotate into a position to engage one of the cables 45-48 and, when the stops 59 fixed to that cable pass beneath the toggle, to drop between them and thereafter prevent further movement of the cable with respect to the messenger frame structure. When all four toggles 61 have thus latched to their respective cables the centering ring 50 is held fixed in the centered position illustrated, and the centering ring will guide the messenger down the main support line in sufficiently good alignment with the array suspended thereby to assure satisfactory operation of the ramp and follower elements 27-29 and also of the latch mechanisms 31-33 next to be described.
Each of these latch mechanisms comprises a latch member 64 pivotally mounted as at 67 to a latch support lever 69 which is in turn pivotally mounted as at 71 between two latch support brackets 72 fixed to the messenger frame structure 35 as shown. Fixed stops 73 and 75 respectively limit the upward and downward rotation of the latch support lever 69, these stops being fixed to the messenger frame structure in any convenient manner. The messenger support cable 21 is pivotally attached to the latch support lever as at 77, with this point of attachment preferably being between the latch pivot axis at 67 and the stop 73 as shown.
The latch mechanisms are self-actuating into latching position as the messenger and array come together. As they do so, each latch pin or bail 33 carried by the array 11 will engage the camming surface 79 of one latch member 65 forcing the latch to rotate, counterclockwise in the case of the lefthand latch and clockwise in the case of the righthand one. The latch pin rides along this camming surface to its end and then drops into the latched position illustrated. Subsequently, as the messenger cables 21 and 23 are tensioned to hoist the assembly surfaceward, the upward pull on the latch support levers 69 serves to more securely engage the latches and, as the latch support levers 69 further rotate, the upward force on the array bail elements 33 will lift the array into engagement with the lower surfaces of the messenger frame structure, thus precluding any possibility of rocking or other relatively movement between the array and messenger during the hoist operation. Bumper pads 81 of rubber or other suitable resilient material may be interposed between the array and messenger to constrain any slight freedom of movement which might remain.
If it is desired that the object be retrieved into a well or hold within the surface vessel as in the illustrated embodiment, positioning of the messenger-array assembly within the well may be provided by a carriage device 83 as shown in FIG. 2. This carriage engages the messenger and array as they are drawn into the well 17 and guides them upwardly either for storage within the hull or topside for repair or other such operations. Carriage 83 is provided with suitable slides or rollers 85 as shown which travel along the bulkheads of well 17 or along vertically disposed guide rails mounted thereto, and its downward movement is limited by a fixed stop 87.
This carriage and well structure as shown also includes provision for automatic control of the messenger centering mechanism and latching devices. As the messenger is hoisted upwardly into engagement with carriage 83, the centering mechanism toggle members 61 contact the underside of the carriage and are pivoted out of engagement between the centering cable stops 59, thus disabling the centering mechanism so long as the messenger remains in this position.
For automatic unlock of the messenger latching devices 31, each is provided with a trip lever assembly comprising a lever member 89 pivotally mounted as at 91 (see FIG. 6) and biased by spring means 93 to a normally horizontal position as illustrated. A follower member 95 which is loaded by spring 97 outwardly with respect to the trip lever 91 engages a trip bar 99 mounted to the adjacent bulkhead of well 17 and is held in engagement therewith by its spring loading irrespective of any small motion of the messenger assembly with respect to the bulkhead. As will be apparent from inspection of FIG. 2, the operation of this latch mechanism is such that when the messenger assembly is being hoisted upwardly into the ship well, the trip lever 89 on striking the trip bar 99 will pivot away from the latch and will not affect it. As the messenger assembly moves downwardly through well 17 during a subsequent launch operation, however, and the trip lever 89 strikes the upper end of trip bar 99, the trip lever is rotated in a direction such that it acts to release the latch thus unlocking the array from the messenger.
While several different operating sequences are possible with the materials handling system of the present invention, the preferred procedure with a sonar array such as illustrated is to retain the messenger adjacent or within the ship hull during the launch operation, and to lower the array using only its main support line 13. As previously mentioned the loading on this cable during launch may be kept acceptably low by permitting a continuous and relatively rapid descent of the array, and after the array is launched and clears the ship there is no problem of their relative alignment.
After launch of the array, the messenger 19 preferably is retained within the ship's hull in engagement with the carriage 83. So long as this engagement continues, the lower frame members of carriage 83 will hold the centering device toggle members 61 in their unlocked position illustrated in FIG. 4B, permitting free play of the cables 45-48 with respect to the messenger frame. This permits the centering ring 50 to follow freely the movement of the main support line 13, with roll and pitch motion of the ship. In this way chafing and flexing of the main support line 13 at its point of contact with centering ring 50 is avoided during the periods when the array hangs suspended at its operating depth below the ship.
For retrieval of the array, the messenger device 19 is dropped downwardly by its support cables 21 and 23, and immediately upon its separation from carriage the centering device toggle members 61 are freed, permitting each to pivot into engagement with its respective centering cables 45-48. These cables now will be moving with the normal motion of the ship in roll and pitch, and within one or two cycles of those motions the stops 59 fixed to each of the centering cables will have moved into latching engagement with the associated toggle member 61, thus locking the centering ring 50 in its central position as illustrated in FIG. 3.
During the further descent of the messenger device 19 centering ring 50 will hold it centered with respect to the main support line 13, so that when the messenger and array come into engagement they will then be in sufficiently close lateral alignment to assure contact of the rollers 43 with the ramp 29, to thus enable this mechanism to rotate the array into angular alignment with the messenger. As such alignment is achieved the latches 31 lock to the bail elements 33 and the assembly thus formed then may be lifted by the messenger cables 21 and 23, the tensioning of which pivots the latch support levers 69 upwardly to firmly lock the array to the messenger for retrieval into the ship well or hold as previously explained.
As will be obvious to those skilled in the art, many modifications to the particular implementation illustrated are possible. For example, the several latching devices illustrated could be controlled manually rather than automatically as shown, and if desired the cooperating parts of the latch assemblies and of the ramp and roller assemblies could be reversed, with those parts shown mounted to the array being instead mounted to the messenger. Other modifications will occur to those skilled in the art and it should be understood that the appended claims are intended to cover all such modifications as fall within the true spirit and scope of the invention. | A handling system for lowering and retrieving large and heavy objects such as sonar arrays from surface ships and other unstable platforms. A submersible object which normally is suspended by a single cable when at operating depth is retrieved and returned to a surface platform by a messenger device suspended on two or more other cables from the platform and provided with means for guiding the messenger to the object, orienting the object with respect to the messenger and thus with respect to the surface platform, and locking the messenger and object together. The resulting messenger and object assembly then may be hoisted back to the platform with some or all of the weight of the assembly carried by the messenger cables thus at least partially unloading the main support cable during retrieval. | 1 |
“This application is a divisional of application Ser. No. 09/607,849, filed Jun. 30, 2000, now U.S. Pat. No. 6,553,971 which application(s) are incorporated herein by reference.”
The present invention relates to a high-pressure pumps with an on-off valve for feeding fuel to an internal combustion engine, particularly a vehicle engine.
BACKGROUND OF THE INVENTION
Various types of high-pressure fuel feed pumps are known, and which are generally supplied with fuel from a normal tank by a low-pressure pump powered by an electric motor. The high-pressure pump normally comprises an on-off valve, which is opened automatically by the fuel fed to it by the low-pressure pump.
The body of known high-pressure pumps encloses at least a fuel compression chamber, and an actuating chamber housing pump actuating members; and the on-off valve comprises a shutter designed to ensure fuel flow to the actuating chamber, even when the valve is closed, to lubricate and cool the actuating members.
In one known radial-piston pump in particular, the pumps body houses three cylinders, in which slide respective pistons activated by a common cam carried by a shaft activated by the drive shaft; the cam is housed inside the actuating chamber or case of the pump; and the shutter is in the form of a hollow cylinder and slides along the wall of a radial hole in the pump body.
The pump body also has a fuel feed conduit for feeding fuel from the radial hole to the cylinders; the feed conduit is closed by the lateral wall of the shutter; and, to lubricate and cool the pump shaft, the cam, and the various pump body and piston friction surfaces, the shutter also has a calibrated axial hole permitting continuous fuel flow to the case.
To prevent fuel accumulating in an engine cylinder, in the event the respective injector breaks down, or to prevent fuel from being drawn from the actuating chamber in the event of poor or no supply by the low-pressure punts e.g. due to a fault, the shutter is closed automatically by a compression spring when the pressure of the incoming fuel falls below a given value.
The compression spring is housed inside the shutter and rests on a perforated plate, which has a surface for receiving the end of the spring and is normally fixed, e.g. welded, to the opposite end of the guide hole of the shutter.
In this known type of pump, machining the radial hole in the pump body, fixing the plate, and assembling the spring are difficult, high-cost operations involving considerable time and highly skilled personnel. Moreover, the perforated plate at the end of the hole facing the case limits to a certain extent the outside diameter of the cam and, hence, the capacity of the pump under given conditions.
SUMMARY OF THE INVENTION
It is an object of the invention to provide an extremely straightforward, reliable high-pressure pump having an on-off valve which is cheap to produce and easy to assemble, so as to eliminate the aforementioned drawbacks of known pumps with on-off valves.
According to the present invention, there is provided a high-pressure pump with an on-off valve for feeding fuel to an internal combustion engine, wherein the pump comprises a body including at least a fuel compression chamber and an actuating chamber enclosing actuating members of said pump, and wherein said valve comprises a shutter sliding inside a hole in said body to close a fuel feed conduit; said feed conduit being formed in said body, between said hole and said compression chamber; and said shutter being held in the closed position by a compression spring; characterized in that said spring rests directly or indirectly on a shoulder inside said hole; said shoulder being formed in one piece with said body.
In a first embodiment of the invention, the spring rests on the shoulder by virtue of means fixed removably inside the hole and comprising a perforated disk inserted removably inside the hole, and an elastic C-shaped metal element located, between the disk and the shoulder, inside an annular groove adjacent to the shoulder.
In a further embodiment of the invention, the spring rests directly on the shoulder, and the wall of the hole has an annular groove permitting precision machining of the wall.
BRIEF DESCRIPTION OF THE DRAWINGS
Two preferred, non-limiting embodiments of the invention will be described by way of example with reference to the accompanying drawings, in which:
FIG. 1 shows a partly sectioned side view of a high-pressure pup with an on-off valve for feeding fuel to en internal combustion engine, in accordance with the invention;
FIG. 2 shows a larger-scale section of the valve and a portion of the pump, according to a first embodiment of the invention;
FIG. 3 shows a larger-scale plan view of a detail in FIG. 2;
FIG. 4 shows a section of a further detail of a variation of FIG. 2;
FIG. 5 shows a larger-scale section of the valve and a portion of the pump, according to a further embodiment of the invention.
DETAILED DESCRIPTION OF THE INVENTION
Number 5 in FIG. 1 indicates as a whole a high-pressure pump for feeding fuel to an internal combustion engine, e.g. of a vehicle. Pump 5 is supplied with fuel from, a normal tank by a low-pressure pump (not shown) powered by an electric motor energized when the engine is turned on.
High-pressure pump 5 is of the type comprising three radial pistons 6 , which slide inside three cylinders 7 arranged radially inside a body 8 of pump 5 ; each cylinder 7 is closed by a plate 9 supporting an intake valve 11 and a delivery valve 12 ; and each cylinder 7 and respective plate 9 are locked to body 8 by a corresponding lock head 13 .
Pistons 6 are activated in sequence by a single cam 14 integral with a shaft 16 powered by the internal combustion engine drive shaft. Cam 14 acts on pistons 6 via a ring 17 having, for each piston 6 , a faced portion 18 cooperating with a shoe 19 fixed to piston 6 ; and each shoe 19 is pushed towards the cam by a corresponding spring 21 .
The gap between the end of each piston 6 and respective plate 9 defines a compression chamber 22 , so that the three compression chambers 22 are obviously housed inside body 8 . The space inside body 8 housing cylinders 7 and in which shaft 16 and cam 14 rotate forms an actuating chamber 23 of pump 5 , which chamber is closed by a flange 24 fixed in known manner to body 8 ; shaft 16 is fitted in rotary and fluidtight manner to flange 24 ; and chamber 23 communicates in known manner with a drain conduit 25 draining into the tank.
Body 8 is made of cast iron, and heads 13 of steel; body 8 and heads 13 have three intake conduits 26 communicating with a conduit defined by an annular groove 27 on flange 24 ; each conduit 26 also communicates with the corresponding compression chamber 22 via corresponding intake valve 11 ; and each head 13 also has a compression conduit 28 , which, via corresponding delivery valve 12 , connects compression chamber 22 to a delivery conduit 29 of pump 5 .
Body 8 also has a feed conduit 30 formed by two holes 31 arranged crosswise to each other and closed outwards by two plugs 32 . At one end, conduit 30 communicates with annular groove 27 of flange 24 and, therefore, with compression chambers 22 ; and, at the other end, conduit 30 comes out at a cylindrical wall 33 of a cylindrical radial hole 34 formed in body 8 . Hole 34 communicates with actuating chamber 23 and projects partly towards flange 24 ; and an inlet conduit 36 connected to the low-pressure pump is inserted inside hole 34 .
Hole 34 houses an on-off valve indicated as a whole by 37 and comprising a hollow, cylindrical shutter 38 . More specifically, shutter 38 is piston- or cup-shaped, and comprises a lateral wall 39 , which slides accurately along wall 33 of hole 34 , so that both wall 33 of hole 34 and wall 39 of shutter 38 must be precision machined.
Shutter 38 also comprises a flat wall 40 , which has a calibrated hole 41 permitting the passage of a certain amount of fuel, even when conduit 30 is closed by shutter 38 . A helical compression spring 42 is inserted inside shutter 38 and rests on a supporting element fixed to the end of hole 34 facing actuating chamber 23 ; and the supporting element must be perforated to permit fuel passage from hole 34 to actuating chamber 23 , as described in Italian Patent Application N. TO95A 000010.
According to the invention, the supporting element of spring 42 is defined by a shoulder 43 of hole 34 , formed in one piece with body 8 and located at the end of hole 34 adjacent to actuating chamber 23 . Shoulder 43 defines a circular opening 45 (FIG. 2) smaller in diameter than hole 34 ; and spring 42 rests directly or indirectly on shoulder 43 , thus simplifying assembly of on-off valve 37 .
In the FIG. 2 embodiment, spring 42 rests on shoulder 43 by virtue of means fixed removably inside hole 34 and comprising a disk 44 having a central opening 46 permitting fuel passage from hole 34 to actuating chamber 23 . Advantageously, the difference in diameter between hole 34 and opening 45 ranges between 1 and 3 mm, and shoulder 43 is of a thickness ranging between 2 and 4 mm.
Opening 46 in disk 44 has a protruding edge 47 for guiding one of the ends of spring 42 ; and disk 44 , together with opening 46 and protruding edge 47 , may be formed cheaply from sheet metal by means of a punching and cold forming or embossing press.
The means fixed removably inside hole 34 also comprise a radially flexible C-shaped metal element 48 , e.g. a standard retaining ring (FIG. 3 ), housed inside hole 34 (FIG. 2 ), between disk 44 and shoulder 43 . More specifically, wall 33 of hole 34 has an annular groove 49 adjacent to shoulder 43 , and into which ring 48 clicks removably and the diameter of opening 45 is such as to enable groove 49 to be machined through opening 45 .
Ring 48 is fitted inside groove 49 or removed from the groove by bringing the two ends of ring 48 together, so that the parts of valve 37 are obviously also easy to assemble, the only precaution being to assemble disk 44 with edge 47 facing spring 42 .
To eliminate even the above precaution and/or simplify automatic assembly of valve 37 , in the FIG. 4 variation, opening 46 of disk 44 may be provided with a ring 51 forming two edges symmetrical with respect to disk 44 and projecting axially in two opposite directions. Ring 51 may be welded to or formed in one piece with disk 44 by compacting and sintering metal powder.
In the FIG. 5 embodiment, spring 42 rests directly on shoulder 43 . Advantageously, the diameter of opening 45 ranges between 3 and 5 mm, and shoulder 43 is of a thickness ranging between 5 and 8 mm. To permit fine machining of wall 33 of hole 34 from outside body 8 , an annular groove 52 is machined in wall 33 , and which may be shallower than groove 49 in FIG. 2, so that valve 37 in FIG. 5 is even cheaper to produce than that in FIG. 2 .
As compared with known pumps, the advantages of the high-pressure pump according to the invention will be clear from the foregoing description. In particular, removable assembly of disk 44 and ring 48 reduces production cost of the pump; shoulder 43 eliminates the need to fix the supporting element of spring 42 inside hole 34 ; and there is no interference between cam ring 17 and the supporting element of spring 42 , so that the diameter of cam 14 can be increased to increase pump capacity.
Clearly, changes may be made to the high-pressure pump as described herein without, however, departing from the scope of the accompanying claims. For example the pistons of pump 5 may be arranged otherwise than as described; and the pump may be applied to other than a vehicle engine. | The pump has a body including at least a fuel compression chamber and an actuating chamber enclosing the actuating members of the pump. The on-off valve has a shutter sliding inside a hole in the body to close a fuel feed conduit. The shutter is held in the closed position by a compression spring, which rests directly or indirectly on a shoulder in the hole. In one embodiment, the spring rests on the shoulder via a perforated disk held by a retaining ring, which clicks removably inside an annular groove in the hole. In a further embodiment, the spring rests directly on the shoulder. | 5 |
This application is a continuation of application Ser. No. 065,458, filed June 23, 1987 now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to seismic vibrators and, more specifically, to a system for monitoring and controlling the hold-down weight of a seismic vibrator.
2. Brief Description of the Prior Art
The currently used seismic p-wave vibrators utilize an actuator to generate a force that is imparted through a baseplate or pad in contact with the surface of the earth. The weight of the vehicle upon which the actuator is installed is used to provide a static force load on the baseplate. If inadequate static force (hold-down) is provided, the baseplate will lose contact with the earth and signal to noise level degradation will occur as a result thereof because harmonic noise is produced when the baseplate loses such contact. This phenomenon is called decoupling. In most vibrators used today, the hold-down force is applied to the baseplate through a system of airbags. The airbags act as acoustic isolators, their low spring rate in conjunction with the mass of the vehicle forming a mass/spring system which has a low resonant frequency, typically less than 2 hertz. The airbag system thus acts as an acoustic isolator, permitting the static force provided by the vehicle weight to be applied to the baseplate but blocking forces generated by the actuator (sweep frequencies are greater than 5 hertz typically) from acting on the vehicle frame.
The vibrator is also equipped with a lift system for raising and lowering of the baseplate. When a sweep is to be generated, the baseplate must be in contact with the earth. The vehicle is jacked up so that as much of the vehicle weight is applied to the baseplate as possible, the wheels generally still contacting the earth. Often, on truck mounted actuators, two or more wheels may actually lose contact with the earth when the vehicle is jacked up.
A sweep interlock system is implemented on all systems currently in use. This interlock system requires the pad (baseplate) to be down before a sweep can be initiated. The interlock systems in current use determine this condition by monitoring the position of the pad with respect to a preset location relative to the vehicle frame or the pad is always lowered to its maximum extension until a mechanical stop is reached. From the standpoint of maximum time savings, it is best to not lower the pad any more than required to achieve adequate hold-down. It takes time to raise and lower the pad (this operation may exceed 1500 times per day). The less stroke used, the less time spent for this operation.
In uneven terrain, the extension required to achieve adequate hold-down is highly variable. For example, if the pad is positioned over a hole but the truck wheels are on high ground, the baseplate must be lowered considerably further to achieve adequate hold-down than in a situation where the baseplate is located over a mound. Also, the current interlock system may indicate the pad is down even though the pad is not in contact with the earth if the pad is over a depression.
A further problem with prior art systems is that the baseplate moves rapidly into the hold-down position, often making forceful contact with the earth and setting up impulses that are later picked up during a seismic test. Also, upon raising the pad after a sweep during the recording time, rapid pad movement can also be a source of unwanted seismic noise as is the noise generated when the vehicle tires come in contact with the earth.
SUMMARY OF THE INVENTION
In accordance with the present invention, the above noted deficiencies of the prior art are minimized. Briefly, this is accomplished by providing a seismic vibrator equipped with airbag isolators, transducer means for monitoring the instantaneous air pressure within the airbags, a summer to add these pressure signals together, a calibrated weighting network to convert the composite pressure for display as hold-down weight on a meter, means for comparing the measured hold-down against a preset threshold that is used to enable or disable sweep generation or operation of an indicator, means for comparing the measured hold-down against a preset threshold that is used as a feedback signal to the lift system, also means for providing a signal proportional to hold-down weight to the sweep generator for use as a feedback signal to modify the amplitude of the force generated by the actuator. As a refinement to the approximation, the actuator weight is accounted for in the summed signal so that its weight is included in the hold-down computation.
The disclosed invention anticipates the use of force transducers like strain gauges or load cells placed on load bearing members of the lift system as an alternate method of monitoring the hold-down force. Also, it is not limited to the use of electrical circuitry for display. Mechanical pressure switches and gauges may also be used.
When the weight of the truck acts upon the airbags, an air pressure increase occurs in the airbags. Typically, the airbags are inflated to 60 psi with no load (there may be chains in tension which limit the amount of airbag dimensional expansion permitted). When weight is applied to the foot piece, the pressure within an airbag will increase to roughly 90 psi on a level surface. Each airbag may be thought of as having an effective piston area, the load borne by an airbag being the product of the pressure and piston area. When the pad is lowered and the airbags compressed, all chains are slack unless operating on a severe incline, thus the effect of the chains can be ignored.
The invention herein offers the potential of increased productivity and better data quality. The time between records provided for moveup can be minimized. The direct display of hold-down will show that roughly 95% of the weight of the truck is applied to the pad before the tires leave the ground. Thus the practice of jacking the vibrator too high just so daylight can be seen will be minimized. Also, it is anticipated that the noise associated with the truck tires hitting the ground will be reduced since there is less potential energy stored in elevating the vibrator too high. Further, in uneven terrain, consistent coupling will be easier to attain.
A further feature of the present invention is the ability to move rapidly to a location close to the hold-down position with slow movement over the final incremental distance to prevent or minimize the possibility of the baseplate striking the ground with sufficient force to set up waves which will erroneously be read during a subsequent test. Also, the invention contemplates decoupling the baseplate from the earth at an initial slow rate with subsequent speed up in the rate of decoupling and lifting of the baseplate.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a diagram of a typical prior art vehicle for transporting and operating a seismic vibrator;
FIGS. 2a and 2B are diagrams of a portion of a prior art vibrator actuator systems using air bags;
FIG. 3 is a block diagram of a seismic vibrator hold-down weight monitor and controller in accordance with a first embodiment of the invention;
FIG. 4 is a block diagram of a seismic vibrator hold-down weight monitor and controller in accordance with a second embodiment of the invention;
FIG. 5 is a block diagram of a seismic vibrator hold-down weight monitor and controller in accordance with a third embodiment of the invention; and
FIG. 6 is a circuit diagram of the circuit of FIG. 3.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
Referring first to FIG. 1, 2A and 2B, there is shown a truck 1 having the standard prior art vibrator actuator 3 mounted thereon. The vibrator actuator 3 is coupled to a baseplate 5 via the stilts 6 to which it is attached and a footpiece 7 for applying the static hold-down force of the truck as shown also in FIG. 2. The static force applied to the baseplate 5 is provided by the weight of the truck and the weight of the actuator system in combination. This force is applied to the baseplate 5 by the truck bed 9 through the lift cylinder 12 resting on intermediate air springs or air bags 11 as shown in FIG. 2. The lift column 10 acts as a guide.
The hydraulic lift cylinder 12 is activated when hydraulic fluid is ported through a valve to raise and lower the actuator/baseplate assembly. The valve is solenoid driven and connected to a hydraulic pump.
In practice, the baseplate is lowered until it contacts the ground and raises the truck chassis, preferably without lifting the wheels off the ground and applying a predetermined static weight or downward force (hold-down) to the baseplate resulting from the weight of the truck and the weight of the actuator system. The actuator is then turned on in a programmed manner to impart acoustic energy to the ground through the baseplate. The acoustic energy imparted by the actuator is less than the hold-down. For example, if there is 40,000 pounds of hold-down, the vibration would be plus or minus 30,000 pounds around that force to avoid decoupling of the base plate with the earth. It is prevention of such decoupling which is one of the features of this invention. This is accomplished by accurately measuring the hold-down force, a measurement not accurately discerned by the prior art, to (1) determine that the baseplate is in contact with the ground and (2) to determine the maximum acoutical energy which can be applied to the baseplate without causing decoupling.
The hold-down force is measured in conjunction with the air bags 11. The air bags are preferably designed to compress to about half of their initial volume by the application of the desired hold-down force thereto. The pressure in the air bags is monitored and, knowing the area of the air bags, a direct reading of the force being applied by the upper assembly or truck bed 9 to the baseplate 5 is obtained. This reading is used in conjunction with other equipment to permit the truck to be lifted off the ground only to the extent necessary to provide the desired hold-down. This reading can also be used to monitor leakage of the air bags and maintain the desired starting conditions therein by causing air to be added or subtracted therefrom. The vibrator actuator system 3 is then set not to exceed this force to prevent decoupling. A standard strain guage pressure transducer (not shown in FIGS. 1 or 2) is provided to measure the pressure in each of the air bags 11. The pressure in the air bags multiplied by the area of the air bags provides a known function of the force being applied thereto as is well known and provides a true reading as opposed to the questionable readings of the prior art.
The pressure information derived from the pressure transducers in the air bags 11 is used to drive the lift cylinder or other devices as described hereinabove in the following manner:
Referring now to FIG. 3, in the preferred embodiment, four air bags are provided, these being front and rear bags on the passenger side and front and rear bags on the driver side. The air bags on the driver side are connected together and the air bags on the passenger side are connected together. Therefore only two sensors are required to determine the pressure on each side of the truck. These sensors are shown as strain gauges 21 and 23.
The input from strain gauges 21 and 23 is summed in summer 25, the output of which is fed to the (-) input of comparators 27 and 29. Resistors 31 and 33 and variable resistor 35 are preset to provide the sweep interlock threshold for comparator 27 whereas resistors 37 and 39 and variable resistor 41 are preset to provide the pad down threshold for comparator 29. The sweep interlock signal induces operation of the vibrator sweep generator whereas the pad down signal operates a switch 43, which can be an FET, a relay or the like to energize the down valve solenoid 45 when the down switch 47 is closed to move the pad down. If the up switch 49 is closed and the down switch 47 is open, the up valve solenoid 51 will be energized to cause the pad to move upwardly. Switch 43 is normally closed whereby, when the pad has gone down sufficiently, the switch 43 will open. This will operate as an inhibit to valve solenoid 45 and prevent further downward movement of the pad. The pad cam switch 49A is normally closed. When the base plate is raised to provide adequate clearance from the ground the pad cam switch contacts are opened to inhibit further upward travel.
When the pad comes down and engages the earth, there is a substantial amount of seismic energy generated thereby which can still be propogating when a test is run. This can cause erroneous readings. This problem also exists upon lifting the pad from the earth. It is therefore desireable to program the lift and/or drop so that there is slow down at the terminal portion of the drop and slow down at the beginning portion of the lift to minimize generation of such seismic energy. This is accomplished with the dual valve lift control system of FIG. 4, wherein like numbers refer to like elements as in FIG. 3. The circuits of FIGS. 3 and 4 are identical through the outputs of comparators 27 and 29.
Switches 61 and 63 are normally closed, switch 61 opening when the voltage at the (+) input of comparator 27 is greater than the voltage at the (-) input thereto, switch 63 opening when the voltage of the (+) input of comparator 29 is greater than the voltage at the (-) input thereto. When the pad down switch 65 is closed, valve solenoids 67 and 69 are energized to cause the pad to be pushed down, such as by porting oil into a cylinder. When the threshold is reached at comparator 27, wherein the (-) input voltage is greater than the (+) input voltage thereto, the switch 61 opens and only relay 69 is energized. This causes pad to be pushed down at a much slower rate, such as by porting or pumping oil into the cylinder at a much slower rate. When the pad has reached its final desired position (adequate hold-down being achieved), the voltage on the (-) input to comparator 29 will be greater than the voltage on the (+) input thereto, thereby opening switch 63 and deenergizing valve solenoid 69. This stops further downward movement of the pad.
For upward movement of the pad, the pad down switch 65 contacts are opened and pad up switch contacts 71 are closed. For the pad up cam switch 72, both sets of contacts are normally closed. Initially, only solenoid L2 will be energized, however, solenoid L2B will not be initially energized because switch 63 will be open due to VS>V1 (full vehicle hold-down weight still rests on the pad). When the baseplate loses contact with the ground, switch 63 will close and both solenoids L2B and L2 will be energized, thereby speeding up the rate at which the baseplate is lifted. Once the pad is lifted to a position allowing adequate ground clearance, the pad up cam switch contacts 72 are opened, de-energizing solenoids L2 and L2B.
Referring now to FIG. 5, there is shown a proportional control circuit. The inputs from the strain gauges 21 and 23 are summed in summer 25 as in the embodiments of FIGS. 3 and 4. The output of the summer is fed to a non-linear function generator 73 which provides an output signal Y which is determined by the value of the input X thereto in accordance with the function as shown. Such circuits are well known and need not be further explained herein. It can be seen that for values of X up to slightly greater than zero, Y is 1 and for large values of X, Y is one-fourth. In the intermediate range, Y drops off linearly from one to one-fourth. Accordingly, for a certain voltage X in to function generator 73, the multiplier 81 provides a product signal output to the summer 83 which is part of a closed loop composed of power amplifier 85, electrohydraulic four-way valve 87 which control positioning of the pad, a linear differential transformer for sensing the valve spool position 88 and linear voltage differential transformer demodulator 89, the closed loop providing a voltage to summer 83 which is proportional to the spool position of the servovalve 87. It follows that, for a certain voltage in to the summer 83, there is provided a certain orifice opening in the servovalve 87. The flow rate through the valve will be proportional to the size of the opening.
It can be seen that the non-linear function 73 will change the rate at which the valve 87 will be opened and/or closed, the function being programmed to correspond to hold-down weight or force. Therefore, if the pad is to go down and switch 77 is closed, when X is a small number, the pad will come down very quickly because Y will be "one" due to large opening of the valve 87. When a predetermined holdown weight is reached where the curve in generator 73 turns downward, Y will gradually decrease to a value of one-quarter and cause the valve 87 to open less or to close more.
The multiplier 81 provides an output Y when there is an input thereto from one of the switches 77 and 79 (i.e., one of switches 77 and 79 is closed). If pad down switch 77 is closed, a positive signal is applied to multiplier 81 along with an initial large Y signal to provide such large signal to amplifier 85 and valve 87 to cause initial rapid opening of the valve and rapid dropping of the pad initially with slowing down of the rate of pad drop as the curve of generator 73 goes from a value of "1" to a value of "one-quarter". If pad up switch 79 is closed, a negative signal is applied to multiplier 81 and causes a negative signal to be applied to valve 87 via amplifier 85 to cause closing of the valve at an initial slow rate with the rate increasing as the curve of generator 73 goes from a value of "one-quarter" to a value of "1" with raising of the pad. The switch 91 is operated by comparator 75 which compares the output of the summer 25 (the holdown force) with a predetermined threshold provided by variable resistor input 93. When the holdown voltage has been reached, the output of comparator 75 will cause switch 91 to open, thereby causing a zero output to be provided by multiplier 81 and causing valve 87 to close.
A circuit diagram of the preferred circuit of FIG. 3 which will accomplish the function of the above described circuits is shown in FIG. 6. Only the driver for energizing coil L1 (45) of FIG. 3 is shown. The signals from the two transducers XDCR #1 and XDCR #2 are summed with resistors 101 and 103 whereby the voltage across capacitor 105 is proportional to the sum of the two pressures. Capacitor 105 removes unwanted transients and acts as a filter. This signal is fed to one input of each of comparators 107 and 109, comparator 107 having its other input providing a reference voltage whereby when the pressure sensed exceeds the reference threshold (the pad is down), transistor 111 lights up a light to indicate that sweep interlock has occurred and provides a signal at output E3 which can be used for the vibrator electronics to indicated that a chirp or vibration can now be commenced since the pad is on the ground with proper hold-down. The other input to comparator 109 provides a reference voltage for a second threshold which is normally higher than the reference threshold for comparator 107 and energized the lift solenoid to lower the pad additionally to achieve an additional hold-down force margin. When full hold-down is achieved, comparator output 109 goes high, turning off transistor 111 (U5-2N2222) and light D2 goes off indicating the down solenoid valve is no longer energized. With transistor 111 off, driver transistor 112 (U6-2N2907) is also off, placing the gate voltage on the FET 114 (IRF9533) at the battery voltage. This turns off the FET and de-energized the down solenoid valve. Switches 113 and 115 are utilized to provide a reading of the pressure on one set of air bags for switch 113 and for the other set of air bags for switch 115. A sum of the pressures is provided if switches 113 and 115 are simultaneously closed.
It can be seen that there has been provided a series of circuits whereby the pad or baseplate of a seismic signal generator system is made to contact the earth with optional changes in the rate of pad drop and/or rise to reduce seismic noise as well as reduce the time required to raise and lower the baseplate, thereby improving productivity.
Though the invention has been described with respect to specific preferred embodiments thereof, many variations and modifications will immediately become apparent to those skilled in the art. It is therefore the intention that the appended claims be interpreted as broadly as possible in view of the prior art to include all such variations and modifications. | The disclosure relates to a seismic vibrator having an airbag isolator, a transducer for monitoring the instantaneous air pressure within the airbags, a summer to add the pressures within each air bag and a calibrated weighting network to convert the composite pressure for display as holdown weight on a meter and for comparing the measured holdown against a preset threshold that is used to enable or disable sweep generation or operation of an inducer. The system also includes structure for comparing the measured holdown against a preset threshold that is used as a feedback signal to the lift system and for providing a signal proportional to holdown weight to the sweep generator for use as a feedback signal to modify the amplitude of the force generated by the actuator. | 6 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to electric lamps having an elongated tubular portion for inserting directly into a lamp mount or reflector base. More particularly, the present invention relates to electric lamps having an elongated tubular portion of a precise, predetermined length with respect to the optical center of said lamp, wherein at least a portion of said tubular portion is inserted directly into and secured in a bore of predetermined length in a plastic lamp mount or reflector so that the optical center of the lamp is at the focal point of the reflector without the need for adjustment, and mount and reflector assemblies containing such lamps.
2. Background of the Disclosure
There is much interest in the automobile industry in using tungsten-halogen lamps and arc lamps as the light sources for automotive headlamps. Tungsten-halogen lamps are presently in such use. Arc lamps have potentially longer life and higher light output and, further, the size of such arc lamps, such as metal halide arc discharge lamps, required for such lighting applications is relatively small, thereby enabling automotive manufacturers a greater leeway in innovative automotive design.
Tungsten-halogen lamps presently employed for automotive lighting in standard sealed beam headlamp units are generally welded to formed wires or posts which are then soldered or brazed to the lamp reflector through electrical feed-through members. Federal regulations are very stringent with regard to strength requirements for lamp sources for replaceable or composite lamps. Accordingly, such lamps are usually retained to a fixture by means of a strap member which is then welded to a metal member for the purpose of focusing and retaining the lamp in the base and in the reflector. U.S. Pat. No. 4,470,104 discloses a means for mounting a tungsten-halogen lamp wherein the lamp, due to temperature and other considerations, is held in place by metal members. Still another means for mounting a tungsten halogen lamp in an automotive type lamp assembly is disclosed in U.S. Pat. No. 4,754,373 in which the lamp is held in place by metal members proximate to the lamp.
In replaceable headlamps the position of the lamp filament relative to the lamp mount inserted into the rear of the reflector must occur within very narrow limits in order to have the focal point of the filament positioned reasonably close to the focal point of the reflector after the lamp and mount assembly are attached to the reflector. To obtain this kind of precision using existing technology, a complicated mounting arrangement is required so that the lamp may be moved relative to the lamp mount or base in order to position the optical center of the lamp within specified limits relative to the mount structure and then welded or otherwise secured to the mount. The lamp and mount assembly is then attached to the reflector in a precise fashion so that the optical center of the lamp corresponds with the focal point or optical center of the reflector. Examples of such complicated lamp mount structures and their use with reflectors are disclosed, for example, in U.S. Pat. Nos. 4,774,645; 4,795,388 and 4,795,936.
In contrast to tungsten-halogen lamps, arc discharge lamps, such as metal halide arc discharge lamps, require extremely high starting voltages, usually in the range of 10,000 to 20,000 volts. Because of these high voltages, it is necessary to electrically isolate the lead wires which exit the quartz or glass lamp envelope. Additionally, some of these lamp designs require very high starting frequencies in the order of 50 kHz in order to initiate the arc and at these high frequencies metallic parts in the proximity of the hot lead wire tend to increase the capacitance of the system. The result of this increased capacitance is to decrease the level of voltage delivered to the lamp for the purpose of initiating the arc. Further, corona discharge sometimes occurs between the hot lead wire and metal parts proximate to the lamp or lead wire. Accordingly, it is therefore desirable to limit the capacitance of the system by removing all but absolutely essential metallic elements from around the lamp. The use of metallic straps around the arc tube seal or otherwise in the proximity of the arc or high voltage lead would reduce the ability of the lamp to start or require higher voltages and, thus, more expensive electronics for starting a lamp in order to compensate for capacitance losses.
Still another phenomena which complicates the use of a scheme for supporting a metal arc discharge lamp relates to sodium loss from the arc chamber. Most arc tubes require compounds of sodium and one or more halogens to enhance their efficiency. Under certain conditions sodium ions can migrate through the quartz (or high temperature glass) arc chamber walls and the corresponding loss of sodium in the lamp results not only in hard starting or failure to start but darkening of the lamp envelope. Sodium migration out of the arc chamber also seems to be enhanced by the presence of metals near the arc chamber. This is a well known phenomenon in the lamp industry and larger metal halide lamps are designed to avoid or minimize the presence of metal near the arc chamber.
SUMMARY OF THE INVENTION
The present invention relates to precision tubulation for self mounting an elongated tubular portion of an electric lamp directly into an electrically non-conductive base or lamp mount. The lamps employed in accordance with the present invention have a vitreous envelope enclosing a filament or electrodes within, with one end of the lamp envelope terminating in an elongated tubular portion of a precise, predetermined length with respect to the optical center of the lamp. By precision tubulation is meant that the lamp is made with the filament or arc electrodes precisely aligned along the axis of the tubular portion and that the tubular portion of the lamp is of a precise, predetermined length with respect to the optical center of the lamp. The tubular portion is inserted directly into and secured in a bore of predetermined length either in the base of a reflector or into a lamp mount without means for adjusting the position of the lamp in either the reflector or the mount. The elongated tubular portion of the lamp will be one end of the vitreous tubing from which the lamp was formed. The hole in the reflector base or lamp mount into which the elongated tubular portion fits is precision molded or machined so that the optical center of the lamp is held in position within the required limits without any need for adjustment of the position of the lamp with respect to the focal point of the reflector once the lamp or lamp and mount assembly is inserted into or attached to the reflector.
In order to achieve this result the tolerance on the length of both the elongated tubular portion of the lamp and the bore into which it is inserted with respect to the optical center of the lamp must be within about ten percent (±10%) of the length of the filament or the length of the arc, the length of the arc being taken as the distance between the arc electrodes. In the case of miniature arc lamps useful with this invention, a typical arc length will range between about 2-3 mm, so that the length of the bore and of the elongated tubular portion of the lamp will be of a combined precision to within a few tenths of a millimeter.
In one embodiment, the present invention relates to an assembly of a lamp and a plastic reflector having an integrally molded base portion wherein said lamp comprises a vitreous envelope containing electrodes or a filament within, said envelope terminating at one end in an elongated tubular portion of a precise, predetermined length with respect to the optical center of said lamp with at least a portion of said tubular portion being inserted directly into a bore in said base of said reflector, said bore and said elongated tubular lamp portion being dimensioned with respect to their lengths such that combined tolerances of said lengths are within ±10% of the length of the arc or filament so that when said lamp is secured within said bore the optical center of said lamp is at about the focal point of said reflector. That portion of the base of the reflector into which the tubular lamp portion is inserted will be constructed of electrically non-conductive and preferably plastic material as an integral part of the reflector. In another embodiment, the lamp will be secured in a bore in a lamp mount which is then secured in a reflector. The length of the bore in both the mount into which the tubular lamp portion is inserted and of the tubular lamp portion with respect to the optical center of the lamp, are dimensioned to have a predetermined length accurate to within about ten percent (±10%) of the arc or filament length. The elongated tubular portion of the lamp may be secured in said bore by means of a press fit, by means of gaskets, set screws, adhesive, collets or chucks, or any combination or other means suitable and made of electrically non-conductive material which is able to withstand the heat transmitted through the lamp tube from the arc or filament.
Means for producing arc lamps and filament containing incandescent lamps such as tungsten-halogen lamps useful in the practice of this invention, and particularly relatively small lamps, have been disclosed, for example, in U.S. Pat. No. 4,810,932 the disclosures of which are incorporated herein by reference. In this patent a method is disclosed for producing arc lamps and double-ended tungsten-halogen incandescent lamps blown from a single piece of lamp tubing and having at least one elongated tubular end. Arc lamps made by this process and having the centering coils described below for centering the arc electrodes have been fabricated having the electrodes radially aligned within three-tenths, two)tenths and even one-tenth of a millimeter of the longitudinal lamp axis and lamp tube. Similarly, incandescent filament lamps have been made with the filament axially aligned to within seven-tenths of a millimeter and even five-tenths (i.e., ±0.5 mm) of a millimeter of the longitudinal lamp axis for a filament ten millimeters long. In making these lamps with such precision radial alignment of the arc electrodes or filament with respect to the longitudinal lamp tube axis, it is particularly preferred that shrink seals and not press seals be employed when hermetically sealing the vitreous lamp envelope during the lamp manufacturing process, as is also disclosed in U.S. Pat. No. 4,810,932.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 schematically illustrates one embodiment of the present invention wherein the elongated tubular portion of an arc discharge lamp is press fit directly into a bore in the base of a plastic reflector.
FIG. 2 represents another embodiment of the invention similar to that of FIG. 1, but where the ground lead of the lamp passes through the base of the reflector instead of through the parabolic reflecting portion.
FIG. 3 schematically illustrates an arc lamp having an elongated tubular portion and electrode centering coils suitable for use with the present invention.
FIG. 4 schematically illustrates another embodiment of the present invention useful for automotive lighting wherein two arc tubes are press fit into the nose or base portions of two combined plastic reflectors associated with an integral housing portion containing electronics for starting and operating the lamps. FIG. 5 schematically illustrates another embodiment of the present invention wherein the tube of a tungsten-halogen lamp is inserted via a press fit into a plastic lamp mount which is mounted on a reflector.
DETAILED DESCRIPTION
Referring now to FIG. 1, there is shown arc lamp 10 comprising arc discharge tube 12 made of vitreous silica (quartz) having an elongated tubular portion 14 supported by a press fit in bore 32 axially extending through a portion of base 34 of plastic parabolic reflector 30 shown in partial, cut-away view. The length of both lamp tube 14 of lamp 10 and bore 32 in the base 34 of reflector 30 are predetermined from the mid point of the arc, defined by the distance between electrodes 18-18', to be of a combined precision within ±10% of the length 18-18', so that when lamp tube 14 seats at wall portion 36 of bore 32, the mid point of arc 18-18' is at about the focal point of reflecting surface 3 (shown in cut-away fashion) of reflector 30. Lamp 10 may also be held in bore 32 in base 34 by any suitable and convenient means such as a relatively high temperature adhesive, a set screw, etc. If an adhesive is used, bore 40 through which hot lead 26 exits base 34 will be large enough to provide an exit for any surplus adhesive or other means may be employed, such as holes or grooves in the bore 32. The bottom of bore 32 terminates in an area of reduced cross section 36 having bore 40 axially extending from the center of bore 32 to the bottom 42 of plastic base 34, thereby providing a path for high voltage lead 26 of lamp 10 which exits through bore 40 for connection to the high voltage end of a starting transformer (not shown). Ground lead 24 of lamp 10 exits through the top portion thereof where it is connected to conductor 28 which extends away from lamp 10 and passes through hole 44 in the reflector portion 38 of reflector 30 for connection to a ground.
FIG. 2 schematically illustrates another embodiment of the present invention wherein lamp 10 is mounted in base portion 34 of reflector 40 in a similar fashion, but wherein ground conductor 28 passes through vitreous tube 46 and out through base 34 for connection to a ground. Vitreous shield 46 is inserted into bore 48 of base 34. Vitreous tube 46 is employed as an insulation shield over conductor 28 because of the closer proximity of conductor 28 to arc tube 10 and hot lead 26. Shield 46 may be made of any suitable vitreous material such as a glass, quartz or a ceramic material. Glass is preferred because it absorbs UV radiation and thus minimizes photon generation at conductor 28 which, because of its proximity to lamp 10 would slowly deplete arc chamber 16 of sodium present therein, thereby shortening the life of the lamp.
FIG. 3 schematically illustrates a particular type of miniature metal halide arc discharge lamp that has been successfully employed in the practice of the present invention. Means for manufacturing such a lamp having an elongated tubular portion as depicted, are known to those skilled in the art and may be found in U.S. Pat. No. 4,810,932 the disclosures of which have been incorporated herein by reference. Turning now to FIG. 3, lamp 10 is illustrated comprising vitreous envelope 12 made of quartz having an elongated tubular portion 14. The lamp contains an arc chamber 16 having electrodes 18 and 18' hermetically sealed therein by means of shrink seals around molybdenum foil members 22 and 22' to which the electrodes are welded. Shrink seals are known to those skilled in the art and an example of how to obtain shrink seals may be found, for example, in U.S. Pat. No. 4,389,20 the disclosures of which are incorporated herein by reference as well as in U.S. Pat. No. 4,810,932. Centering coils 20 and 20', made out of a suitable high temperature material such as tungsten, insure precision radial alignment of the electrodes within the arc chamber. Top projecting lead wire 24 is connected to the other end of molybdenum foil seal 22 and bottom projecting lead wire 26, which is the high voltage lead, is shown projecting through and exiting the elongated portion 14 of lamp 10.
FIG. 4 schematically illustrates yet another embodiment of the present invention wherein the elongated tubular portions 14 and 14' of lamps 10 and 10' are inserted directly into bores 32 and 32' of integrally molded plastic base portions 34 and 34' in reflectors 30 and 30' in a fashion similar to that described for the integral reflector mount in FIGS. 1 and 2. High voltage lamp leads 26 and 26' are shown connected to high voltage transformers 90 and 90', shown in partial cut-away fashion, which are contained in housing 80 which forms an integral part of overall lamp assembly 100. Lens portion 90 is hermetically sealed to assembly 100. Ground leads 28 and 28' of lamps 10 and 10' exit through reflector walls 38 and 38' into housing 80 wherein they are connected to a suitable ground (not shown).
Turning now to FIG. 5, lamp 11 comprises a vitreous quartz or high temperature aluminosilicate glass envelope 13 having a filament chamber 15 enclosing tungsten filament 17 connected at opposite ends to molybdenum inlead wires 19 and 19' and having an elongated tubular portion 21. Lamp 11 is supported in a precision molded bore or hole 43 in plastic mount 41. The bottom of bore 43 terminates in an area of reduced cross section 45 having another bore (not shown) extending from the center of 45 into base 41 for connecting hot lead 23 to a source of electricity (not shown) in a standard fashion. Ground lead 25 of lamp 11 exits through the top portion thereof where it is connected to conductor 27 which passes through a bore 51 in mount 41. Molybdenum foils 29 and 29' are shrink sealed into the envelope 13 to provide a hermetic seal and an electrical path from inlead 23 to ground lead 25. Mount 41 is attached to base 35 of reflector 31 by mounting tabs molded as an integral part of said base of which two, 47 and 47', are illustrated in the Figure. Locking tabs in base 35, illustrated by 49 and 49' , serve to secure the mount in the base as is known to those skilled in the art.
Arc lamps having vitreous silica (quartz) envelopes generally operate at inner envelope wall temperatures of about 750-900° C., whereas tungsten-halogen lamps having high temperature glass envelopes operate at about 300-700° C. and higher if quartz envelopes are used. Accordingly, the plastic into which the elongated tubular lamp portion is inserted will be made of an electrically non-conductive plastic material capable of being molded or machined and having sufficient heat resistance to be able to be used with the present invention without being distorted or melted from the heat emitted by the arc and also conducted from the arc chamber of the lamp by the lamp tube 14. Suitable high temperature resistant plastics include materials such as Teflon, polysulfones, liquid crystal polymers, such as Vectra A130 by Celanese Corporation, polyetherimides such as Ultem by GE and polyphenylene sulfides such as Supec by GE and Ryton by Philips. | An electric lamp fabricated from lamp tubing and terminating at one end in an elongated tubular portion which is of a precise, predetermined length with respect to the optical center of the lamp is inserted directly into and held in a bore in the rear of a reflector so that the optical center of the lamp is at the focal point of the reflector without need for adjusting the position of the lamp in the reflector. | 5 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention resides in the field of time-delayed, automatic shut-off means for valves.
2. Prior Art
Generally, automatic shut-off means for valves such as exemplified by U.S. Pat. Nos. 2,181,581 (Fraser); 2,710,736 (Miller) 3,065,948 (Nolan) and 3,342,448 (Parkison) have characterized the prior art in this area.
All of the aforementioned patents, incorporate a time-delay mechanism which utilizes, as the metered liquid, the same liquid as controlled by the valve whose time-delayed closing is regulated by the dashpot mechanism.
In most applications, this liquid will be water. Use of water as the dashpot metering liquid typically results in minerals being deposited in and about the passageway through which the liquid is metered.
At the very least, the mineral deposits will restrict the effective diameter of the liquid metering passageway thereby increasing the time delay. Eventually, the metering passageway becomes plugged rendering the dashpot mechanism inoperative.
To remedy this situation, some of the prior art devices utilized a movable pin which moved in and out of the metering passageway to clear it of the restricting mineral deposits.
However, even the use of a pin to create a so-called "self-cleaning orifice" is inadequate to effect a reliable dashpot device which uses the water from the water supply because within a very short period of time the mineralization will clog the liquid metering combination and thereby render it inoperative.
Further, the solid particles within the water will, if not filtered, be deposited within the dashpot chamber and either completely fill it, or at the very least, unduly limit the stroke of the dashpot piston. In either case, the time delay is significantly shortened or becomes effectively "zero."
In addition, the viscosity of water acts as a practical limit on the amount of time delay available in a dashpot device such as found in the aforementioned patents.
Utilizing a liquid for dashpot metering other than water in a water supply system obviously requires that the metering liquid be isolated from the water supply system. However, one of the problems encountered when using a liquid other than water as the dashpot liquid is that during the operation of the dashpot a small amount of the dashpot liquid is lost. Eventually, the dashpot liquid becomes exhausted to such an extent that the dashpot becomes inoperative.
Further, the liquid selected for use as the dashpot liquid must have a rather large heat capacity to preclude it from being converted into its gaseous phase when the dashpot mechanism is used with a hot water supply. Should this occur, the dashpot time-delay would be reduced and/or the fluid seals may be unable to adequately contain the metering fluid in its gaseous phase.
SUMMARY OF THE INVENTION AND OBJECTS
An adjustable dashpot mechanism is disclosed which is particularly useful for controlling the rate of return of a spring-loaded, axially-displaceable stem for a liquid-control valve. The dashpot mechanism is conveniently assembled in the form of a cartridge-like assembly and is removably attachable to the liquid-control valve housing. When so attached, the stem of the dashpot mechanism is placed in abutment with the axially-displaceable valve stem.
Fundamentally, the dashpot mechanism comprises a housing, a dashpot piston with a flexible flange thereabout and fixedly mounted on a hollow stem, and arranged to conformably mate with the inside of the housing wall, a passageway with a variable crossectional area which places the inside of the hollow stem in fluid communication with both piston faces and a spring-biased reservoir piston slidably mounted on the stem and disposed above the dashpot piston in fluid-sealing engagement with the inside of the housing wall.
Prior to operation of the dashpot, the cartridge housing is removably secured to the valve housing in order to place the end of the hollow stem in abutting engagement with the stem of the axially-displaceable valve and then the dashpot and reservoir chambers are filled with timing liquid via a threaded aperture in the reservoir piston. The valve is typically maintained in its closed position by a compression spring disposed about the valve stem.
When the opposite end of the dashpot piston-stem is depressed, the timing liquid in the dashpot chamber is forced around the flexible flange and piston into the dashpot chamber located between the reservoir piston and the dashpot piston. A small amount of the timing liquid will pass through the passageway through the piston, but this amount is insignificant compared to the amount of liquid which flows past the flexible flange.
The spring-biased, floating reservoir piston is then directed into engagement with the surface of the timing liquid ensuring that the relatively incompressible timing liquid is captured in an enclosure having a fixed volume.
Since the valve spring is compressed when the valve is opened, the valve stem exerts a force on the piston stem directing the piston towards the reservoir piston. When this occurs, the flexible peripheral flange expands outwardly and forms an annular, U-shaped cup which prevents the timing liquid from flowing thereabout by creating a fluid seal between the rigid piston body and the inner wall of the dashpot housing. Consequently, the timing liquid is directed into the passageway through the piston and stem body. By metering this liquid through the passageway, the rate at which the piston stem returns into the dashpot housing is delayed. The rate of delay is controlled by the rate of timing liquid flow through the passageway. The rate of timing liquid flow is, of course, in turn, controlled by the effective liquid flow area which is a function of the cross-sectional area of the passageway.
When the valve stem is depressed to open the valve, the fluid seal which isolates the timing liquid from the valve-controlled liquid, typically water, wipes the timing liquid from the stem. However, since a small amount of the timing liquid remains as a residue on the stem body as it extends out of the cartridge body, a small amount of timing fluid is lost during each cycle. Consequently, to extend the operational life of the dashpot time-delay function, a supplemental supply of timing liquid is contained in a reservoir within the housing to automatically replenish the supply of dashpot timing liquid as it is lost.
This invention is particularly useful when combined with water faucets to create a time-delayed, automatic-closing faucet for use in public facilities and institutions.
An object of the invention is to provide a new and improved self-closing faucet arranged so that the time-delayed closing action of the valve is repetitive at a constant rate irrespective of variations in water supply or inlet pressures.
A further object of the present invention is to provide a novel automatically-closing faucet having a dashpot timing device removably connectable to a valve via a split stem.
Another object of the invention is to provide a combination time-delayed closing unit and valve wherein the piston is arranged to retard the closing movement of the valve while allowing rapid opening movement when the valve stem is manually displaced in an axial fashion to open the valve.
The various features of novelty which characterize our invention are pointed out with particularity in the claims annexed to and forming a part of the specification. However, in order to obtain a more complete understanding of the present invention, along with its attendant advantages and features, and specific objects obtained through its use, reference should be had to the accompanying drawings and detailed description of the preferred embodiment hereinafterwards described and illustrated.
The accompanying drawings illustrate a preferred embodiment of the invention, in which:
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a split-elevational view of the present invention, shown partially in section, the left side depicting said invention in its closed position and the right half depicting said invention in an open or fully extended position.
FIG. 2 is a partial elevational section of the stem-mounted, dashpot piston element of the present invention the left side depicting the dashpot piston in its substantially unactuated postion and the right side depicting the dashpot piston following the actuation thereof at the start of the time-delay cycle.
FIG. 3 is an elevational section of the stem and piston member of the present invention with the variable liquid metering passageway illustrated in its open position.
FIG. 4 is similar to FIG. 3 with the liquid metering passageway depicted in its closed position.
FIG. 5 is a partial elevational section of the spring-biased, reservoir piston mounted on the stem of the dashpot stem and piston member of the present invention the left side depicting the location of the reservoir piston when the reservoir is substantially filled with timing liquid and the right side depicting the location of the reservoir piston when the reservoir is substantially depleted of timing liquid.
Before explaining the instant invention in detail, it is to be understood that the invention is not limited by way of its application to the details of construction and arrangement of parts as illustrated in the accompanying drawings. This is so because the invention is capable of other embodiments and of being practiced in various ways. It should also be clearly understood that the phraseology or terminology utilized herein is primarily directed towards the purpose of description and should not be considered as a limitation thereon.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIG. 1 of the drawings, the present invention referred to and indicated generally at 10, comprises, in general, a housing 63, a dashpot piston 58 with a flexible flange or an annular check valve and fluid-sealing member 61 thereabout and fixedly mounted on a hollow stem 57, an adjustable, liquid metering passageway 59 for effecting fluid communication between the oppositely-disposed piston faces 12, 13 and a spring-biased reservoir piston 8 slidably mounted to the stem 57 and disposed above the piston 58, and a push button member 14 secured to the stem 57 to permit manual actuation of the instant invention.
As clearly shown in FIG. 1, the present invention 10 is shown in its assembled form and is threadably secured to a water supply pipe 15 about the threaded section 16 of the necked-down, upstanding section 17 of the water pipe 15. Immediately below the upstanding section 17, the water pipe 15 is increased in diameter to form an enlarged chamber area which is divided into a water inlet chamber 18 and a water outlet chamber 19 by an internal annular shoulder 20. The face of the shoulder 20 facing the water outlet chamber 19 is countersunk to form a beveled seating surface 21.
Turning now to the valve cartridge 11, said cartridge 11 comprises a generally cylindrically-shaped body 22, and a spring 23 and a poppet valve member 24. The outside diameter of the body 22 is smaller than the inside diameter of the upstanding section 17 of the water pipe 15 and is adapted to be slidably inserted thereinto in substantial fluid-sealing relationship therewith. The inside of the body 22 is generally characterized throughout a major portion of its length by a relatively smooth bore having a constant cross section. However, adjacent to the bottom end 25 of the body 22, the body 22 is abruptly tapered, in an inwardly-directed fashion, to form a beveled surface 26 for fluid sealing engagement with the seating surface 21 of the shoulder 20. The surface at the bottom end 25 inside the body 22 is spotfaced to form an annular shoulder 27. The rim forming the bottom end 25 of the body 22 is radiused and extends beyond and beneath the seating surface 21 to form a valve seat 28.
The coil spring 23 has a diameter which is smaller than the inside diameter of the body 22 so as to be coaxially installable therein. When placed inside the body 22, the bottom end of the spring 23 rests on the shoulder 27 which serves as a stop for one end of the spring 23.
Intermediate the top end 29 and the bottom end 25 of the valve cartridge body 22, two oppositely-disposed apertures 30 are drilled through the wall of said body 22. These apertures 30 allow continuous fluid communication between the water outlet chamber 19 and the inside of the valve cartridge body 22.
The poppet valve member 24 comprises a stem 31, a valve head, generally indicated at 32 and centrally disposed at the bottom end of said stem 31 and a flange member 33 centrally disposed at the top of the stem 31. Intermediate the top and bottom ends the stem 31, a hole 34 is drilled transversely through the longitudinal axis of the stem 31. A rod (not shown) is aligned with holes 30, 34 and passed therethrough to lock the valve in its open position to permit the removal and replacement of the ring 9.
The valve head 32, in turn, is formed by an elastomeric ring 9 with an annular, beveled valve face 35 about the edge of one of its radially-extending faces, said ring 9 slidably mated over the undercut section 36 of the stem 31 with the beveled face 35 facing the top end of the stem 31. In addition, the beveled face 35 side of the ring 9 is abutted against the outwardly-extending, stepped radial wall 37. This wall 37 serves to support one end of the valve face 35 in order to prevent the ring 34 from being stretched and thereafter rolled over. Without wall 37, this typically occurs when the valve face 35 is engaged and disengaged with the valve seat 28. When it rolls over, the valve face 35 will not seat properly with the valve seat 28 and will typically leak.
The bottom of the ring 9 is nested in an annular, U-shaped cup 38 which is mounted on the end of stem 31 about the undercut section 36. The cup 38 provides support for the elastomeric ring 9 so as to allow the ring 9 to achieve proper seating with the valve seat 28. The end of the stem 31 is bored and threaded to form a receptacle 39 for a threaded fastener. A threaded fastener 40, having a crown portion 41 larger in diameter than the aperture of the annular cup 38, is threadably mated with the receptacle 39 to prevent the cup 38 from sliding off the undercut section 36.
The annular flange member 33 has a diameter which is slightly smaller than the inside diameter of the valve cartridge body 22. This allows the flange member 33 to be slidably mated with the relatively smooth bore of the body 22. The function and purpose of the flange member 33 is fully developed as the present invention is further described hereinafterwards.
The valve cartridge 11 is easily assembled in the following manner. The spring 23 is inserted, bottom end first, into the body 22 and rests on the shoulder 27. The stem 31 of the poppet valve member 24, without the valve head 32, is inserted into the body 22 undercut section 36 first. At the same time, the top end of the spring 23 engages the underside of the flange member 33 and serves as a stop therefor. The ring 29 is now fitted over the end of the stem 31 about the undercut section 36. The U shaped annular cup 38 is then slidably mated with the undercut section 36 of the stem 31 and placed in intimate abutment with the elastomeric ring 28. Following this, the threaded fastener 40 is threadably mated with the receptacle 39 thereby securing the valve head assembly in fixed relationship to the stem 31.
It should be noted at this time that in the assembled configuration, the flange member 33 serves to function in a number of necessary roles. First of all, it serves as a surface against which an axial force can be applied to overcome the bias force of the spring 23, thereby allowing the valve head 32 to move away from the valve seat 28. Secondly, the sidewall 42 of the flanged surface 33 is sufficiently deep to prevent deviation of the stem 31 from the longitudinal axis of the valve cartridge body 22 especially during actuation thereof. Such a deviation is oftentimes referred to as "cocking." The desired flange thickness necessary to prevent cocking may be calculated by using the well-known mathematical formula for non-cocking; namely, that the effective length of the guided vertical distance when divided by the diameter of the flange 33 should be at least unity or one. In this case, the effective length of the guided vertical distance is equal to the thickness or depth 42 of the flange member 33. Consequently, the flange member 33 serves to guide the stem, and, therefore, the valve head 32, so as to ensure that the valve head 32 is engaged and disengaged with the valve seat 28 in a poppet valve fashion. Thirdly, the diameter of the flange member 33 is sufficiently small with respect to the bore diameter of the body 22 to permit fluid, such as water, to pass freely therebetween.
Once the valve cartridge 11 is assembled, it is installed into the upstanding section 17 of the water pipe 15, bottom end 25 first, and seated in fluid sealing relationship with the seating surface 21 of the shoulder 20. When seated, the apertures 30 are located within the water outlet chamber 19 allowing fluid communication between the inside of the body 22 and the chamber 19. Further, when the cartridge body 22 is seated, the top end 43 of the body 22 projects beyond the top of the upstanding water pipe section 17.
A fluid-sealing gasket 44 is slidably mated over the top end 43 of the body 22 and thereafter seated against the rim 45 of the upstanding water pipe section 17.
The housing 63 is threadably secured to the upstanding section 17 of the water pipe 15 about a threaded section 16 of a cylindrical skirt 110 with a wrench-gripping surface 11 thereabout and depending from the housing 63 so as to securely fix and seat the valve cartridge body 22 against the seating surface 21 within the water pipe 15 and to simultaneously effect a fluid seal between the gasket 44 and the housing 63. When this is accomplished, the end 65 of the stem 64 is disposed in juxtaposition to the spotface 66 of the top end 29 of the poppet valve member 24. The spotface 66 locates the stem 64 in axial alignment with the poppet valve member 24.
Referring now also to FIG. 2, an annular fluid sealing member 67 is disposed in a groove 7 in the housing 63 to prevent leakage of liquid from the housing 63. A snap-ring 69 about the end 65 of the stem 64 serves to prevent the stem 64 from being disengaged from the housing 63 and to limit the travel of the piston member 58.
The chamber 71 within the housing 63 is functionally separated into two chambers; namely, a dashpot chamber 70 and a reservoir chamber 72. The dashpot chamber 70 houses a dashpot piston member 58 which is typically formed as an integral part of the stem 64 and positioned intermediate the ends thereof. A groove 68 about the outer edge of the piston 58 serves as a receptacle for the flexible flange 61 which is disposed in conformal relationship to the inside wall of the housing 63 which functions as an annular check valve and fluid sealing member 61 during the operation of the invention.
The flexible flange 61 is typically fabricated from an elastomeric material, such as rubber, neoprene, plastic or the like. The annular flange 61 has a generally V shaped cross section. The inside leg 75 of the flange 61 is constructed for intimate abutment with the bottom of the groove 7, and is formed so that the bottom of the leg 75 extends to the outer edge of the lower groove wall 73.
By radially projecting the lower groove wall 73 beyond the upper groove wall 74 and by positioning the notch of the V in the flange 61 above the lower groove wall 73 and within the radius thereof, greater operational stability and control of the flexible flange 61 is achieved.
Turning now to FIG. 5, the reservoir chamber 72 area is detailed, and contains a second piston member 8 which is slidably mounted onto the upper portion of the stem 64. A groove 77 about the inner opening of the second piston member 8 serves as a seat for a fluid sealing member 78; typically an elastomeric O-ring seal. Thus, a fluid seal is effected between the inner opening of the second piston member 8 and the stem 64. A second groove 79 about the periphery of the piston 8 serves as a receptacle for a second fluid sealing member 80 to create a fluid seal between the housing 63 in the reservoir chamber 72 and the second piston member 8.
A helically-wound spring 81 is installed between the inwardly-projecting flange 82 rimming the upper portion of the housing 63 and the upper piston face 83. A threaded passageway 85 bored through the body of the second piston member 8 permits, when desired, fluid communication between the areas divided by the second piston member 8. A screw 84 and an annular fluid-sealing gasket 86 are used to plug the passageway 85 when desired. The purpose and need for the passageway 85 and the screw 84 will become apparent as the description of the present invention continues.
With continued reference now to FIGS. 3 and 4, it may be seen that the stem 64 is tubular in nature. The upper portion 87 of the stem 64 is threaded. The balance of the tubular stem 64 has a smooth surface 88. A passageway 89 is bored from the junction of the piston face 12 into the hollow stem 64. Another passageway 90 is bored from the junction of the piston face 13 into the hollow stem 64. Together with the hollow portion of the stem 64, passageways 89,90 form a passageway 59 the function of which will become more apparent as the description of the instant invention proceeds.
A solid, rod-like body 91 having an upper, threaded section 92 and a lower, smooth-surfaced section 93 with three annular grooves 94, 95 and 96 thereabout, whose function will be described hereinafterwards, is threadably mated with the threaded, upper portion 87 of the stem 64. The lower, smooth-surface section 93 is slidably and peripherally mated with the smooth surface 88 of the stem 64.
Annular, O-ring type, fluid seals 97 and 98 are seated in the grooves 94 and 96 respectively, and effect a fluid sealing relationship between the lower section 93 and the smooth surface 88 of the stem 64.
It should be noted at this time that the degree of threaded engagement between the threaded section 87 of the stem 64 and the threaded section 92 of the body 91 may be adjusted via the recessed portion 99 in the top of the body 91. Typically, the recessed portion 99 will be hex-shaped in order to accept an Allen wrench. The degree of threaded engagement will, of course, provide the necessary means by which the body 91 may be effectively reciprocated within the stem 64, to vary the degree of alignment between the groove 95 and the passageways 89,90, the purpose of which is hereinafterwards described.
Returning once again to FIG. 1, it may be seen that a cup-shaped cap 14 having a boss 102 slidably engaged with the top end of the stem 64 and a threaded aperture 103 in the wall of the boss 102 is fixedly secured to the top end 100 of the stem 64 via the annular groove 101 in the stem 64, by means of a set-screw 104 which is threadably engaged with the threaded aperture 103 and projects therebeyond into the groove 101 of the stem 64. The cap 14 functions as a push button member 14 to effect axial displacement of the stem 64 when desired. Apertures 105, 106 in the push button member 14 serve to respectively provide access to the set screw 104 and the recessed portion 99 of the body 91 to permit either the removal or adjustment thereof.
Prior to operation of the subject invention, the screw 84 is removed from the threaded passageway 85 of the piston 8. The timing liquid, typically liquid silicon, such as A Dimethylpolysiloxane, is injected into the housing chamber disposed between the two pistons 58, 8 until this chamber is completely filled with liquid. The stem 64 is then axially-displaced to cycle the piston 58 throughout its entire stroke in order to ensure that both the reservoir chamber 72 and the dashpot chamber 70 are completely filled with the timing liquid. However, when a syringe is used to inject the timing fluid into the chambers 70 and 72, the syringe needle is slipped between flange 61 and the wall of the housing 63 to first fill the dashpot chamber 70 and afterwards the needle is withdrawn into the reservoir chamber 72 to fill the reservoir chamber 72. Filling in this manner does not require any cycling or movement of the dashpot piston 58 and its stem 31. Once this is done, the screw 84 is replaced to plug the passageway 85. With continued reference to the drawings it may be seen that the operation of the present embodiment of the subject invention is effectuated by manually depressing the push button member 14. As is clearly shown in FIG. 1, the left side depicts the present invention coupled to a poppet valve; both of which are shown in a closed position. The right side illustrates the present invention coupled to a poppet valve; both of which are shown in an open position. The depression of the push button member 14 produces an inward displacement of the stem 64 which, in turn, contacts the top end 29 of the poppet valve member 24 and produces a corresponding inward displacement of the poppet valve member 24 thereby unseating the beveled valve face 35 of the valve head 32 from the valve seat 28.
When the valve face 35 is unseated, water flows from the water inlet chamber 18 into the water outlet chamber 19 via the unseated valve head 35 and the valve seat 28. This unseated condition is illustrated by the right-hand side, in vertical section, of FIG. 1.
As the valve face 35 is unseated, the silicon timing liquid in the chamber 71 of the housing 63, as a result of the piston movement of the dashpot piston member 58, the timing liquid forces the peripheral lip of the flange 61 towards the leg 75 thereby permitting the liquid to flow relatively unrestrictedly into the housing chamber between the dashpot piston member 58 and the second piston member 8. Additionally, an insignificant amount of the timing liquid enters the passageway 89 and flows into the tubular stem 64 about the groove 95 in the body 91 and out of the passageway 90 into the housing chamber between the piston member 58 and the second piston member 8.
When the face 12 of the dashpot piston member 58 contacts the housing 63 adjacently-disposed about the groove 68, the push button member 14 is released. Since the spring 23 about the poppet valve member 24 is compressed as clearly shown in the right-hand side of FIG. 1, a bias is applied to the stem 64 tending to direct the dashpot piston member 58 towards the second piston member 8. As the dashpot piston member 58 begins to move in this direction, the silicon timing liquid forces the periphal lip of the flange 61 outwardly and into fluid sealing engagement with the housing 63. As a result, the timing liquid cannot flow from the housing chamber disposed between the dashpot piston member 58 and the second piston member 8 via the flange 61 into the housing chamber located between the dashpot piston member 58 and the housing 63 adjacently-disposed about the groove 68. Consequently, the timing liquid is forced to flow thereinto via the metering passageway 59. The liquid metering passageway 59 comprises passageway 90, the passageway formed between the tubular stem 64 and the annular groove 95 and passageway 89, as shown in FIG. 3. Annular, O-ring-type fluid seals 97 and 98, which are seated in grooves 94 and 96 respectively, act to contain the timing liquid within the liquid metering passageway 59.
The rate at which the dashpot piston member 58 travels toward the second piston member 8 is determined by the rate at which the timing liquid flows through the metering passageway 59. The timing liquid flow rate through the liquid metering passageway 59 is primarily determined by the cross-sectional area of the metering passageway 59. In this particular embodiment of the present invention, the cross-sectional area is determined by the degree of alignment between the two passageways 89 and 90 and the annular groove 95 in the body 91. Due to this particular function, the body 91 is generally referred to as a timing screw.
As illustrated in FIG. 4, the timing screw 91 may be adjusted to completely block the flow of timing liquid through the liquid metering passageway 59.
Adjustment of the timing screw 91 is typically accomplished by the use of an Allen wrench adapted to be received into the recessed portion 99 in the top of the timing screw 91.
Concurrently with the movement of the dashpot piston member 58, the silicon timing liquid disposed in the housing chamber between the dashpot piston member 58 and the second piston member 8 is maintained in full liquid contact with the metering passageway 59 by the second piston member 8 which is biased towards the dashpot piston member 58 by means of the spring 81. Consequently, the chamber 72 acts as liquid reservoir for the dashpot chamber 70, serving to replenish the timing liquid which is lost as the lower portion 65 of the stem 64 is wiped by the annular fluid seal 67 as it exists the housing 63 when the push button member 14 is depressed. Following the wiping of the stem 64 by the seal 67, a residue is left on the lower portion 65 of the stem 64 which represents a small loss of silicon timing liquid. Therefore, to prolong the operational life of the present invention, a reservoir chamber is required to insure that an additional amount of silicon liquid timing fluid is provided.
The reservoir chamber area 72 is characterized, in this particular embodiment of the present invention, by its slightly larger bore in the housing 63 as compared to the bore of the dashpot chamber area 70. Since the reservoir piston member 8 is peripherally engaged with the walls about the bore of the reservoir chamber area 72, the stepped annular section 107 serves as a stop to prevent the reservoir piston member 8 from traveling therebeyond and into the dashpot chamber area 70. Absent such a stop, the operation of the dashpot piston member 58 might be limited or impaired. Further, by limiting the travel of the reservoir piston member 8, the spring 81 is always maintained in compression even when the reservoir piston member 8 is stopped against the stepped annular section 107 as illustrated in the right-hand section of FIG. 5, thereby continously providing a positive spring bias force to the reservoir piston member 8 to insure full contact with the timing liquid in the reservoir chamber area 72.
When the reservoir piston member 8 is at the opposite extreme of its travel within the reservoir chamber area 72, as shown in the left-hand section of FIG. 5, the helically-wound spring 81 is near fully compressed and acts as a stop to prevent the reservoir piston member 8 from traveling therebeyond.
While the instant invention has been described with reference to a particular embodiment thereof, it will be readily understood that variations and modifications thereof may be made without departing from the spirit or scope of the instant invention. | An adjustable dashpot mechanism for controlling the rate of return of a spring-biased axially-displaceable shaft, comprising: a tubular housing having portions of unequal diameters therein with rims thereabout a shaft slidably mounted within the housing and extending beyond the ends of the housing, a dashpot piston fixedly mounted to the shaft within the housing and having an adjustable orifice therethrough, a flexible flange disposed between the periphery of the dashpot piston and the housing for effecting fluid sealing engagement therebetween when the dashpot piston is moved away from the smaller diametered portion in the housing and for effecting nonfluid sealing engagement when the dashpot piston is moved towards the smaller diametered portion in the housing, a reservoir piston slidably mounted on the shaft within the housing between the larger diametered portion of the housing and the dashpot piston and a spring disposed between the housing and the reservoir piston for urging the reservoir piston towards the dashpot piston. | 5 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to a buckle device of a car seatbelt system which is controlled by a passenger when fastening a webbing.
2. Background Information
A conventional buckle device is designed such that a single tongue plate is inserted thereinto to obtain an engaged state.
When a plurality of webbings or belts are used, a corresponding plurality of tongue plates are made insertable into buckle devices (see, Japanese Patent Application Laid-Open No. 61-37107).
With this type of buckle device, a pair of tongue plates is inserted into a buckle body in a crossing mode to obtain an engaged state. To release the tongue plates from the engaged state, a release button must be pushed by the occupant in the thicknesswise direction of the buckle body that is orthogonal to the insertion direction of the tongue plates. Thus, the release button must be operated with a large operational force while holding the buckle body between the fingers.
SUMMARY OF THE INVENTION
It is an object of the present invention to provide a buckle device capable of engaging a plurality of tongue plates which is configured so that the tongue plates can be readily released from an engaged state.
A buckle device according to the present invention includes a release button made movable in a plane defined by the insertion directions of the tongue plates, and when pushed, releases the tongue plates from their engaged state. A cam-contact mechanism, a link mechanism, or the like is used to transmit a force from the release button to lock members for engaging the tongue plates.
Specifically, the moving direction of the release button is confined in the plane defined by the insertion directions of the tongue plates; therefore, only upon pushing the release button with a finger, the tongue plates are disengaged. Generally, a buckle body is supported to a vehicle body in such a manner that the buckle body can bear the reactive force of the insertion of the tongue plates; therefore, the tongue plates can be inserted in the buckle body without the need to hold the buckle body by hand. This is also effective when pushing/moving the release button to release the tongue plates, that is, the buckle body can bear the reaction of moving the release button without the need to hold the buckle body in ones hand.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a sectional view showing a first embodiment of a buckle device according to the present invention, in which tongue plates are in an engaged state;
FIG. 2 is a sectional view similar to FIG. 1, in which the tongue plates are in a released state;
FIG. 3 is an exploded perspective view showing the first embodiment;
FIG. 4 is a sectional view showing a second embodiment of the buckle device, in which the tongue plates are in the engaged state;
FIG. 5 is a sectional view similar to FIG. 4, in which the tongue plates are in the released state;
FIG. 6 is an exploded perspective view showing the second embodiment; and
FIG. 7 is a schematic front view showing a link mechanism used in the second embodiment.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
FIGS. 1 through 3 show a first embodiment of the present invention in which tongue plates are released by the use of a cam.
In a buckle device of this embodiment, a plate-shaped buckle body 12 has a support opening 14 formed in an end portion thereof, which serves as an attaching portion of an attaching strap 16 secured to a body of a vehicle (not shown). Provided around the periphery of the attaching strap 16 is a sleeve-shaped cover 18 having a certain rigidity. The buckle device is disposed in the inside the car cabin in an upright position. The attaching strap 16 itself may also be made from a rigid support material.
As seen in FIG. 3, the buckle body 12 has a slit 22 formed in an end portion thereof opposite to the support opening 14, which extends substantially orthogonal to the wise direction of the support opening 14. Portions of the buckle body 12 between the slit 22 and the support opening 14 spread radially from the vicinity of the support opening 14 to define extension portions 24 and 26. These extension portions 24 and 26 are folded back, leaving curved upright portions 24A and 26A, and then extend parallel to the buckle body 12. Each of the curved portions 24A and 26A has an opening 28 formed therein through which tongue plates 32, 34 can be inserted, respectively. The tongue plates 32 and 34 are arranged symmetrically with respect to the slit 22, to which fastening webbings 36 and 38 are attached. Therefore, an occupant can put on the two fastening webbings 36 and 38 together.
Each of the tongue plates 32 and 34 is guided at one edge by a rivet 42 when it is inserted into the buckle body 12. The rivets 42 are included to secure the buckle body 12 and the extension portions 24, 26 together. Each of the tongue plates 32 and 34 has a notch 32A, 34A opposite to the rivet 42, into which a pair of lock bars 44 is fitted.
That is, the tongue plates 32 and 34 can be inserted into the buckle body 12 in the directions of the arrows A and B, respectively, that are angularly spaced from each other by an angle of about 90 degrees. To make the lock bars 44 movable orthogonally to the insertion directions of the tongue plates 32 and 34, guide holes 46 are formed in the extension portions 24 and 26 of the buckle body 12. Spring seats 48 are secured between the buckle body 12 and the extension portions 24 and 26, and compression springs 52 are interposed between the lock bars 44 and the spring seats 48, so that the lock bars 44 are urged in the directions in which they enter into the insertion paths of the tongue plates 32 and 34. Therefore, when the tongue plates 32 and 34 are inserted through the openings 28, the lock bars 44 are shifted in respective separating directions from the insertion paths of the tongue plates 32 and 34 by means of inclined surfaces 32B and 34B formed at the ends of the tongue plates 32 and 34. Then, by virtue of the urging force of the compression springs 52, the lock bars 44 are fitted in the notches 32A and 34A to keep the tongue plates 32 and 34 in an engaged state.
To urge the tongue plates 32 and 34 thus inserted in the buckle body 12 in respective ejection directions, torsion springs 54 are provided.
A slide release button 56 is movably fitted into the slit 22 of the buckle body 12. Specifically, the release button 56 is integrally molded from synthetic resin such that when it is moved along the middle line between the tongue plates 32 and 34 (in the direction of the arrow C) while being guided by the slit 22, the two tongue plates 32 and 34 are released from the engaged state. In this regard, the release button 56 has parallel extension portions 56A and 56B which pass along either surface of each of the tongue plates 32 and 34 inserted and engaged. Each of the parallel extension portions 56A and 56B has an oblique surface 58 which is inclined at substantially 45 degrees in the insertion direction of the release button 56. Therefore, when the release button 56 is pushed in the direction of the arrow C, each oblique surface 58 shifts the corresponding lock bar 44 through a cam-contact action in opposition to the urging force of the compression coil spring 52. The angle of inclination of the oblique surface 58 may be changed such that the lock bar 44 is pushed by a force stronger than that applied to the release button 56.
As shown in FIG. 3, the buckle body 12 is enclosed by an upper cover 62 and a lower cover 64 connected together, and a control portion 56C of the release button 56 projects through an opening 62A formed in the upper cover 62, which is controlled by the occupant.
The operation of the embodiment will be described.
When the passenger inserts the tongue plates 32 and 34 through the corresponding openings 28, the lock bars 44 are engage with the notches 32A and 34A by virtue of the urging force of the compression coil springs 52, so that the tongue plates 32 and 34 are held in an engaged state. At this time, since the buckle body 12 is held in the upright position on the body by means of the attaching strap 16 and the cover 18, it is not necessary to hold the buckle body 12 by fingers or the like during the insertion operation of the tongue plates 32 and 34 in the directions of the arrows A and B. That is, the reaction of insertion is surely borne by the attaching strap 16 and the cover 18, this eliminating the need to apply any supporting force to the buckle body 12.
On the other hand, when wanting to release the fastening webbings 36 and 38, the occupant pushes the release button 56 in the direction of the arrow C. Consequently, the oblique surfaces 58 of the release button 56 engages with the lock bars 44 to push the lock bars 44 out of the notches 32A and 34A, so that the lock bars 44 are removed from the moving paths of the tongue plates 32 and 34 and thus the tongue plates 32 and 34 are released from their engaged state. In this case, since the reaction of the moving of the release button 56 pushed in the direction of the arrow C is borne by the attaching strap 16 and the cover 18 as is the case of the insertion operation of the tongue plates 32 and 34, the operation needed for the passenger is only to push the release button 56 in the direction of the arrow C and it is not necessary to hold or grip the buckle body 12.
FIGS. 4 through 6 shows a second embodiment of the present invention in which tongue plates are released by the use of a link mechanism.
In this embodiment, a pair of buckle bodies 82 and 84 is superposed and secured together by rivets 86, and the superposed section of the buckle bodies 82 and 84 has a support opening 14 formed therein.
Each buckle body 82, 84 has a radially-extending base extension portion 88, 92, a curved portion 94, and a folded-back parallel extension portion 96, 98 which is parallel to the corresponding base extension portion 88, 92. Each parallel extension portion 96, 98 has a folded engaging piece 102 at an edge portion thereof, and each folded engaging piece 102 has a fastening piece 104 at the end thereof which is designed to abut on the outer surface of the base extension portion 88, 92, so that the parallel extension portion 96, 98 and the base extension portion 88, 92 are prevented from coming apart from each other by means of the folded engaging portion 102 with the fastening piece 104.
The space between the folded engaging pieces 102 and the curved portions 94 defines insertion portions for the tongue plates 32, 34. The insertion directions (of the arrows A and B) are arranged so as to cross each other in the combination of buckle bodies 82 and 84 as in the case of the first embodiment.
Spring seats 106 are secured between the base extension portions 88, 92 and the parallel extension portions 96, 98. Compression coil springs 108 are interposed between the spring seats 106 and lock bars 112 such that the lock bars 112 are fitted into notches 32A, 34A of the tongue plates 32, 34. The lock bars 112 are combined integrally with a holder 114. The holders 114 are slidably received into openings 116 formed in the base extension portions 88, 92 and in the parallel extension portions 96, 98 so that the lock bars 112 can move smoothly. The lock bars 112 are made from metal to so as to have a large supporting force.
The spring seats 106 have hook portions 106C and 106D formed integrally in the arm portions 106A and 106B thereof. These hook portions 106C and 106D are resiliently engaged in openings 88A and 102A formed in the extension portions 88, 96, 92, 98 and in the folded engaging pieces 102 to retain the spring seats 106.
A release button 122 is disposed so as to shift in the direction of the arrow C or along the middle line between the directions of the arrows A and B. In this embodiment, the release button 122 is formed into a sectionally U-shaped plate, which has pins 124 projecting coaxially in opposite directions. One end of each of the pair of links 126 and 128 is pivotally supported by the pins 124. The other ends of these links 126 and 128 are pivotally supported to one of the ends of links 132 and 134. The other ends of the links 132 and 134 are pivotally supported by a rivet 136 provided upright on the buckle bodies 82 and 84.
The links 126, 128, 132 and 134 are all the same length, thus defining a parallelogram. The pivot sections of the links 126 and 132 and the links 128 and 138 correspond to protruding portions 112A of the lock bars 112 supported by the extension portions 88, 92, 96 and 98.
Therefore, when the release button 122 is pushed in the direction of the arrow C, two opposite vertexes of the parallelogram corresponding to the pins 124 and the rivet 136 approach each other and the other two opposite vertexes separate from each other; therefore, the lock bars 112 are moved in opposition to the urging force of the compression coil springs 108 to come out of engagement with the tongue plates 32, 34.
FIG. 7 schematically shows the relationship between the pushing force of the release button 122 and the operating force applied from the links 126, 128, 132, 134 to the lock bars 112. The illustrated parallel link mechanism forms a toggle boosting mechanism. Where the pushing direction (of the arrow C) of the release button 122 is orthogonal to the working direction of the operation force acting on the lock bars 112, when an angle θ corresponding to one-half of the interior angle between the links 126 and 132 is no greater than 45 degrees, the pushing operation force of the release button 122 is magnified and applied to the lock bars 112. That is, letting F1 be the operation force of the release button 122 and F3 be the working force acting on the lock bars 112, the following expression holds:
F3=F1 cotθ (1)
When the angle θ is 30 degrees, F3 becomes F1.7 times of F1, that is, the engaged state of the tongue plates 32, 34 can be released with a small operation force. In this embodiment, when the working direction of the working force F3 deviates from the moving direction of the lock bars 112, such a deviation causes some loss, resulting in some change in magnification.
In this embodiment, also, the operation direction (of the arrow C) of the release button 122 is confined in a plane defined by the insertion directions of the pair of tongue plates 32 and 34; therefore, if the attaching strap 16 and the cover 18 included in the first embodiment for bearing the reactive force of insertion of the tongue plates 32 and 34 are used in the second embodiment no additional means for bearing the reactive of operation is required, making it very easy to operate the buckle device. | A buckle device for a car seatbelt system is used together with a plurality of tongue plates to which occupant securing webbings are connected. Lock members for engaging the tongue plates are released upon operating a single release button. The shifting direction of the release button is confined in a plane defined by the insertion directions of the tongue plates. The operation force of the release button is transmitted to the lock members via a mechanism for example cam-contact or link mechanism. Therefore, the operation necessary for a passenger at the time of release is only to push the release button. There is no need to hold or pinch the buckle device at any time. | 8 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a divisional of application Ser. No. 09/921,615, filed Aug. 3, 2001, now U.S. Pat. No. 6,632,736, issued Oct. 14, 2003, which is a continuation of application Ser. No. 09/495,534, filed Jan. 31, 2000, now U.S. Pat. No. 6,291,340, issued Sep. 18, 2001, which is a continuation of application Ser. No. 09/012,685, filed Jan. 23, 1998, now U.S. Pat. No. 6,081,034, issued Jun. 27, 2000, which is a continuation of application Ser. No. 08/509,708, filed Jul. 31, 1995, now U.S. Pat. No. 5,723,382, issued Mar. 3, 1998, which is a continuation-in-part of U.S. application Ser. No. 08/228,795, filed Apr. 15, 1994, now abandoned, which is a continuation of now abandoned U.S. application Ser. No. 07/898,059, filed Jun. 12, 1992 now abandoned.
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention relates to integrated circuit manufacturing technology and, more specifically, to structures for making low-resistance contact through a dielectric layer to a diffusion region in an underlying silicon layer. The structures include an amorphous titanium nitride barrier layer that is deposited via chemical vapor deposition.
2. State of the Art
The compound titanium nitride (TiN) has numerous potential applications because it is extremely hard, chemically inert (although it readily dissolves in hydrofluoric acid), an excellent conductor, possesses optical characteristics similar to those of gold, and has a melting point around 3000° C. This durable material has long been used to gild inexpensive jewelry and other art objects. However, during the last ten to twelve years, important uses have been found for TiN in the field of integrated circuit manufacturing. Not only is TiN unaffected by integrated circuit processing temperatures and most reagents, it also functions as an excellent barrier against diffusion of dopants between semiconductor layers. In addition, TiN also makes excellent ohmic contact with other conductive layers.
In a common application for integrated circuit manufacture, a contact opening is etched through an insulative layer down to a diffusion region to which electrical contact is to be made. Titanium metal is then sputtered over the wafer so that the exposed surface of the diffusion region is coated. The titanium metal is eventually converted to titanium silicide, thus providing an excellent conductive interface at the surface of the diffusion region. A titanium nitride barrier layer is then deposited, coating the walls and floor of the contact opening. Chemical vapor deposition of tungsten or polysilicon follows. In the case of tungsten, the titanium nitride layer provides greatly improved adhesion between the walls of the opening and the tungsten metal. In the case of the polysilicon, the titanium nitride layer acts as a barrier against dopant diffusion from the polysilicon layer into the diffusion region.
Titanium nitride films may be created using a variety of processes. Some of those processes are reactive sputtering of a titanium nitride target; annealing of an already deposited titanium layer in a nitrogen ambient; chemical vapor deposition at high temperature and at atmospheric pressure, using titanium tetrachloride, nitrogen and hydrogen as reactants; and chemical vapor deposition at low-temperature and at atmospheric pressure, using ammonia and Ti(NR 2 ) 4 compounds as precursors. Each of these processes has its associated problems.
Both reactive sputtering and nitrogen ambient annealing of deposited titanium result in films having poor step coverage, which are not useable in submicron processes. Chemical vapor deposition (CVD) processes have an important advantage in that conformal layers of any thickness may be deposited. This is especially advantageous in ultra-large-scale integrated circuits, where minimum feature widths may be smaller than 0.5 μm. Layers as thin as 10 Å may be readily produced using CVD. However, TiN coatings prepared using the high-temperature atmospheric pressure CVD (APCVD) process must be prepared at temperatures between 900-1000° C. The high temperatures involved in this process are incompatible with conventional integrated circuit manufacturing processes. Hence, depositions using the APCVD process are restricted to refractory substrates such as tungsten carbide. The low-temperature APCVD, on the other hand, though performed within a temperature range of 100-400° C. that is compatible with conventional integrated circuit manufacturing processes, is problematic because the precursor compounds (ammonia and Ti(NR 2 ) 4 ) react spontaneously in the gas phase. Consequently, special precursor delivery systems are required to keep the gases separated during delivery to the reaction chamber. In spite of special delivery systems, the highly spontaneous reaction makes full wafer coverage difficult to achieve. Even when achieved, the deposited films tend to lack uniform conformality, are generally characterized by poor step coverage, and tend to deposit on every surface within the reaction chamber, leading to particle problems.
U.S. Pat. No. 3,807,008, which issued in 1974, suggested that tetrakis dimethylamino titanium, tetrakis diethylamino titanium, or tetrakis diphenylamino titanium might be decomposed within a temperature range of 400-1,200° C. to form a coating on titanium-containing substrates. It appears that no experiments were performed to demonstrate the efficacy of the suggestion, nor were any process parameters specifically given. However, it appears that the suggested reaction was to be performed at atmospheric pressure.
In U.S. Pat. No. 5,178,911, issued to R. G. Gordon, et al., a chemical vapor deposition process is disclosed for creating thin, crystalline titanium nitride films using tetrakis-dimethylamido-titanium and ammonia as precursors.
In the J. Appl. Phys. 70(7) October 1991, pp 3,666-3,677, A. Katz and colleagues describe a rapid-thermal, low-pressure, chemical vapor deposition (RTLPCVD) process for depositing titanium nitride films, which, like those deposited by the process of Gordon, et al., are crystalline in structure.
BRIEF SUMMARY OF THE INVENTION
This invention constitutes a contact structure incorporating an amorphous titanium nitride barrier layer formed via low-pressure chemical vapor deposition (LPCVD) utilizing tetrakis-dialkylamido-titanium, Ti(NMe 2 ) 4 , as the precursor. Although the barrier layer compound is primarily amorphous titanium nitride, its stoichiometry is variable, and it may contain carbon impurities in amounts which are dependent on deposition and post-deposition conditions. The barrier layers so deposited demonstrate excellent step coverage, a high degree of conformality, and an acceptable level of resistivity. Because of their amorphous structure (i.e., having no definite crystalline structure), the titanium nitride layer acts as an exceptional barrier to the migration of ions or atoms from a metal layer on one side of the titanium carbonitride barrier layer to a semiconductor layer on the other side thereof, or as a barrier to the migration of dopants between two different semiconductor layers which are physically separated by the barrier layer.
The contact structure is fabricated by etching a contact opening through a dielectric layer down to a diffusion region to which electrical contact is to be made. Titanium metal is deposited over the surface of the wafer so that the exposed surface of the diffusion region is completely covered by a layer of the metal. Sputtering is the most commonly utilized method of titanium deposition. At least a portion of the titanium metal layer is eventually converted to titanium silicide, thus providing an excellent conductive interface at the surface of the diffusion region. A titanium nitride barrier layer is then deposited using a low-pressure chemical vapor deposition (LPCVD) process, coating the walls and floor of the contact opening. Chemical vapor deposition (CVD) of polycrystalline silicon, or of a metal, such as tungsten, follows, and proceeds until the contact opening is completely filled with either polycrystalline silicon or the metal. In the case of the polysilicon, which must be doped with N-type or P-type impurities to render it conductive, the titanium nitride layer acts as a barrier against dopant diffusion from the polysilicon layer into the diffusion region. In the case of CVD tungsten, the titanium nitride layer protects the junction from reactions with precursor gases during the CVD deposition process, provides greatly improved adhesion between the walls of the opening and the tungsten metal, and prevents the diffusion of tungsten atoms into the diffusion region.
Deposition of the titanium nitride barrier layer takes place in a low-pressure chamber (i.e., a chamber in which pressure has been reduced to less than 100 torr prior to deposition), and utilizes a metal-organic tetrakis-dialkylamido-titanium compound as the sole precursor. Any noble gas, as well as nitrogen or hydrogen, or a mixture of two or more of the foregoing, may be used as a carrier for the precursor. The wafer is heated to a temperature within a range of 200-600° C. Precursor molecules which contact the heated wafer are pyrolyzed to form titanium nitride containing variable amounts of carbon impurities, which deposits as a highly conformal film on the wafer.
The carbon content of the barrier film may be minimized by utilizing tetrakis-dimethylamido-titanium, Ti(NMe 2 ) 4 , as the precursor, rather than compounds such as tetrakis-diethylamido-titanium or tetrakis-dibutylamido-titanium, which contain a higher percentage of carbon by weight. The carbon content of the barrier film may be further minimized by performing a rapid thermal anneal step in the presence of ammonia.
The basic deposition process may be enhanced to further reduce the carbon content of the deposited titanium nitride film by introducing one or more halogen gases, or one or more activated species (which may include halogen, NH 3 , or hydrogen radicals) into the deposition chamber. Halogen gases and activated species attack the alkyl-nitrogen bonds of the primary precursor and convert displaced alkyl groups into volatile compounds.
As heretofore stated, the titanium carbonitride films formed by the instant chemical vapor deposition process are principally amorphous compounds. Other processes currently in use for depositing titanium nitride-containing compounds as barrier layers within integrated circuits result in titanium nitride having crystalline structures. As atomic and ionic migration tends to occur at crystal grain boundaries, an amorphous film is a superior barrier to such migration.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
FIG. 1 is a block schematic diagram of a low-pressure chemical vapor deposition reactor system;
FIG. 2 is an X-ray spectrum (i.e., a plot of counts per second as a function of 2-theta);
FIG. 3 is a cross-sectional view of a contact opening having a narrow aspect ratio that has been etched through an insulative layer to an underlying silicon substrate, the insulative layer and the contact opening having been subjected to a blanket deposition of titanium metal;
FIG. 4 is a cross-sectional view of the contact opening of FIG. 3 following the deposition of an amorphous titanium nitride film;
FIG. 5 is a cross-sectional view of the contact opening of FIG. 4 following an anneal step; and
FIG. 6 is a cross-sectional view of the contact opening of FIG. 5 following the deposition of a conductive material layer.
DETAILED DESCRIPTION OF THE INVENTION
The integrated circuit contact structure that is the focus of this disclosure is unique because of the use of a predominantly amorphous titanium or titanium carbonitride barrier layer therein. The layer is deposited using a low-pressure chemical vapor deposition (LPCVD) process that is the subject of previously filed U.S. patent applications as heretofore noted.
The LPCVD process for depositing highly conformal titanium nitride and titanium carbonitride barrier films will now be briefly described in reference to the low-pressure chemical vapor deposition reactor system depicted in FIG. 1 . The deposition process takes place in a cold wall chamber 11 . A wafer 12 , on which the deposition will be performed, is mounted on a susceptor plate 13 , which is heated to a temperature within a range of 200-600° C. by a heat lamp array 14 . For the instant process, a carrier gas selected from a group consisting of the noble gases and nitrogen and hydrogen is bubbled through liquid tetrakis-dialkylamido-titanium 15 (the sole metal-organic precursor compound) in a bubbler apparatus 16 .
It should be noted that tetrakis-dialkylamido-titanium is a family of compounds, of which tetrakis-dimethylamido-titanium, tetrakis-diethylamido-titanium and tetrakis-dibutylamido-titanium have been synthesized. Because of its lower carbon content per unit of molecular weight, tetrakis-dimethylamido-titanium is the preferred precursor because it results in barrier films having lower carbon content. However, any of the three compounds or any combination of the three compounds will result in highly conformal barrier layers when pyrolyzed (decomposition by heating) in a CVD deposition chamber. These barrier layers are characterized by an amorphous structure, and by step coverage on vertical wall portions near the base of submicron contact openings having depth-to-width aspect ratios of 3:1 that range from 80-90 percent of the horizontal film thickness at the top of the opening.
Still referring to FIG. 1 , the carrier gas, at least partially saturated with a vaporized precursor compound, is transported via a primary intake manifold 17 to a premix chamber 18 . Additional carrier gas may be optionally supplied to premix chamber 18 via supply tube 19 . Carrier gas, mixed with the precursor compound, is then ducted through a secondary intake manifold 20 to a shower head 21 , from which they enter the chamber 11 . The precursor compound, upon coming into contact with the heated wafer, pyrolyzes and deposits as a highly conformal titanium carbonitride film on the surface of the wafer 12 . The reaction products from the pyrolysis of the precursor compound are withdrawn from the chamber 11 via an exhaust manifold 22 . Incorporated in the exhaust manifold 22 are a pressure sensor 23 , a pressure switch 24 , a vacuum valve 25 , a pressure control valve 26 , a blower 27 , and a particulate filter 28 , which filters out solid reactants before the exhaust is vented to the atmosphere. During the deposition process, the pressure within chamber 11 is maintained at a pressure of less than 100 torr and at a pressure of less than 1 torr by pressure control components 23 , 24 , 25 , 26 , and 27 . The process parameters that are presently deemed to be optimum, or nearly so, are a carrier gas flow through secondary intake manifold 20 of 400 standard cubic centimeters per minute (scc/m), a deposition chamber temperature of 425° C., and a flow of carrier gas through bubbler apparatus 16 of 100 scc/m, with the liquid tetrakis-dialkylamido-titanium 15 being maintained at a constant temperature of approximately 40° C.
Thus, the carrier gas (or gases) and the vaporized precursor compound are then gradually admitted into the chamber until the desired pressure and gas composition is achieved. The reaction, therefore, takes place at a constant temperature, but with varying gas partial pressures during the initial phase of the process. This combination of process parameters is apparently responsible for the deposition of titanium carbonitride having a predominantly amorphous structure as the precursor compound undergoes thermal decomposition. The X-ray spectrum of FIG. 2 is indicative of such an amorphous structure. Both the peak at a 2-theta value of 36, which is characteristic of titanium nitride having a (111) crystal orientation, and the peak at a 2-theta value of 41, which is characteristic of titanium nitride having a (200) crystal orientation, are conspicuously absent from the spectrum. Such a spectrum indicates that there is virtually no crystalline titanium nitride in the analyzed film. Incidentally, the peak at a 2-theta value of 69 is representative of silicon.
Although the compound deposited on the wafer with this process may be referred to as titanium carbonitride (represented by the chemical formula TiC x N y ), the stoichiometry of the compound is variable, depending on the conditions under which it is deposited. The primary constituents of films deposited using the new process and tetrakis-dimethylamido-titanium as the precursor are titanium and nitrogen, with the ratio of nitrogen atoms to carbon atoms in the film falling within a range of 5:1 to 10:1. In addition, upon exposure to the atmosphere, the deposited films absorb oxygen. Thus the final film may be represented by the chemical formula TiC x N y O z . The carbon and oxygen impurities affect the characteristics of the film in at least two ways. Firstly, the barrier function of the film is enhanced. Secondly, the carbon and oxygen impurities dramatically raise the resistivity of the film. Sputtered titanium nitride has a bulk sheet resistivity of approximately 75 μohm-cm, while the titanium carbonitride films deposited through the CVD process disclosed herein have bulk sheet resistivities of 2,000 to 50,000 μohm-cm. In spite of this dramatic increase in bulk resistivity, the utility of such films as barrier layers is largely unaffected, due to the characteristic thinness of barrier layers used in integrated circuit manufacture. A simple analysis of the contact geometry for calculating various contributions to the overall resistance suggests that metal (e.g., tungsten) plug resistance and metal-to-silicon interface resistance play a much more significant role in overall contact resistance than does the barrier layer.
There are a number of ways by which the basic LPCVD process may be enhanced to minimize the carbon content of the deposited barrier film.
The simplest way is to perform a rapid thermal anneal step in the presence of ammonia. During such a step, much of the carbon in the deposited film is displaced by nitrogen atoms.
The basic deposition process may be enhanced to further reduce the carbon content of the deposited titanium nitride film by introducing an activated species into the deposition chamber. The activated species attacks the alkyl-nitrogen bonds of the primary precursor and converts displaced alkyl groups into volatile compounds. The activated species, which may include halogen, NH 3 , or hydrogen radicals, or a combination thereof, are generated in the absence of the primary precursor at a location remote from the deposition chamber. Remote generation of the activated species is required because it is not desirable to employ a plasma CVD process, as Ti(NR 2 ) 4 is known to break down in plasma, resulting in large amounts of carbon in the deposited film. A high carbon content will elevate the bulk resistivity of the film to levels that are unacceptable for most integrated circuit applications. The primary precursor molecules and the activated species are mixed, preferably, just prior to being ducted into the deposition chamber. It is hypothesized that as soon as the mixing has occurred, the activated species begin to tear away the alkyl groups from the primary precursor molecules. Relatively uncontaminated titanium nitride deposits on the heated wafer surface.
Alternatively, the basic deposition process may be enhanced to lower the carbon content of the deposited titanium nitride films by introducing a halogen gas, such as F 2 , Cl 2 or Br 2 , into the deposition chamber. The halogen gas molecule attacks the alkyl-nitrogen bonds of the primary precursor compound molecule and converts the displaced alkyl groups into a volatile compound. The halogen gas is admitted to the deposition chamber in one of three ways. The first way is to admit halogen gas into the deposition chamber before the primary precursor compound is admitted. During this “pre-conditioning” step, the halogen gas becomes adsorbed on the chamber and wafer surfaces. The LPCVD deposition process is then performed without admitting additional halogen gas into the deposition chamber. As a first alternative, the halogen gas and vaporized primary precursor compound are admitted into the deposition chamber simultaneously. Ideally, the halogen gas and vaporized primary precursor compound are introduced into the chamber via a single shower head having separate ducts for both the halogen gas and the vaporized primary precursor compound. Maintaining the halogen gas separate from the primary precursor compound until it has entered the deposition chamber prevents the deposition of titanium nitride on the shower head. It is hypothesized that as soon as the mixing has occurred, the halogen molecules attack the primary precursor molecules and begin to tear away the alkyl groups therefrom. Relatively uncontaminated titanium nitride deposits on the heated wafer surface. As a second alternative, halogen gas is admitted into the chamber both before and during the introduction of the primary precursor compound.
As heretofore stated, the titanium nitride or titanium carbonitride films deposited by the described LPCVD process are predominantly amorphous compounds. Other processes currently in use for depositing titanium nitride-containing compounds as barrier layers within integrated circuits result in titanium nitride having crystalline structures. As atomic and ionic migration tends to occur at crystal grain boundaries, an amorphous film is a superior barrier to such migration.
Referring now to FIG. 3 , which is but a tiny cross-sectional area of a silicon wafer undergoing an integrated circuit fabrication process, a contact opening 31 having a narrow aspect ratio has been etched through a borophosphosilicate glass (BPSG) layer 32 to a diffusion region 33 in an underlying silicon substrate 34 . A titanium metal layer 35 is then deposited over the surface of the wafer. Because titanium metal is normally deposited by sputtering, it deposits primarily on horizontal surfaces. Thus, the portions of the titanium metal layer 35 on the walls and at the bottom of the contact opening 31 are much thinner than the portion that is outside of the opening on horizontal surfaces. The portion of titanium metal layer 35 that covers diffusion region 33 at the bottom of contact opening 31 will be denoted 35 A. At least a portion of the titanium metal layer portion 35 A will be converted to titanium silicide in order to provide a low-resistance interface at the surface of the diffusion region.
Referring now to FIG. 4 , a titanium nitride barrier layer 41 is then deposited utilizing the LPCVD process, coating the walls and floor of the contact opening 31 .
Referring now to FIG. 5 , a high-temperature anneal step in an ambient gas such as nitrogen, argon, ammonia, or hydrogen is performed either after the deposition of the titanium metal layer 35 or after the deposition of the titanium nitride barrier layer 41 . Rapid thermal processing (RTP) and furnace annealing are two viable options for this step. During the anneal step, the titanium metal layer portion 35 A at the bottom of contact opening 31 is either partially or completely consumed by reaction with a portion of the upper surface of the diffusion region 33 to form a titanium silicide layer 51 . The titanium silicide layer 51 , which forms at the interface between the diffusion region 33 and titanium metal layer portion 35 A, greatly lowers contact resistance in the contact region.
Referring now to FIG. 6 , a low-resistance conductive layer 62 of metal or heavily-doped polysilicon may be deposited on top of the titanium nitride barrier layer 41 . Tungsten or aluminum metal is commonly used for such applications. Copper or nickel, though more difficult to etch than aluminum or tungsten, may also be used.
Although only several embodiments of the inventive process have been disclosed herein, it will be obvious to those having ordinary skill in the art that modifications and changes may be made thereto without affecting the scope and spirit of the invention as claimed. | A contact structure is provided incorporating an amorphous titanium nitride barrier layer formed via low-pressure chemical vapor deposition (LPCVD) utilizing tetrakis-dialkylamido-titanium, Ti(NMe 2 ) 4 , as the precursor. The contact structure is fabricated by etching a contact opening through a dielectric layer down to a diffusion region to which electrical contact is to be made. Titanium metal is deposited over the surface of the wafer so that the exposed surface of the diffusion region is completely covered by a layer of the metal. At least a portion of the titanium metal layer is eventually converted to titanium silicide, thus providing an excellent conductive interface at the surface of the diffusion region. A titanium nitride barrier layer is then deposited using the LPCVD process, coating the walls and floor of the contact opening. Chemical vapor deposition of polycrystalline silicon or of a metal follows. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to cable length compensation in a measurement device and, in particular, to cable length compensation in a capacitance versus voltage (CV) analyzer that employs an auto-balanced bridge technique.
2. Description of Related Art
It is known to use an auto-balanced bridge technique in a measurement device to measure an alternating current (AC) impedance of a device under test (DUT). It is further known to manufacture cables for use with the measurement device that have a target phase delay, and to compensate for the phase delay in analyzing the DUT. It would be desirable to provide a measurement device that employs an auto-balanced bridge technique and that can directly measure the phase delay of an unknown attached cable, and compensate for the phase delay when analyzing a DUT.
BRIEF SUMMARY OF THE INVENTION
A transmission line impedance compensation method includes the step of providing a measurement device that is adapted to source a test signal having a frequency to a device under test and to determine a corresponding impedance of the device under test using an auto-balanced bridge technique. A first transmission line, a second transmission line, a third transmission line, and a fourth transmission line are connected to said measurement device. An end of the first transmission line is connected to an end of second transmission line. An end of third transmission line is connected to an end of fourth transmission line. A phase delay of the connected first and second transmission lines, and a phase delay of the connected third and fourth transmission lines, are measured by the measuring device. The device under test is connected to the first transmission line, the second transmission line, the third transmission line, and the fourth transmission line after measuring the phase delays. The corresponding impedance of the device under test is determined based on both of the phase delays.
An impedance meter for determining the impedance of a device under test includes a first source terminal for connecting the impedance meter to the device under test, a first sense terminal for connecting the impedance meter to the device under test, a second source terminal for connecting the impedance meter to the device under test, and a second sense terminal for connecting the impedance meter to the device under test. The impedance meter is adapted to determine an electrical length of a first transmission line connected to at least one of said terminals.
Another transmission line impedance compensation method includes the step of providing a measurement device that is adapted to source a test signal having a frequency to a device under test and to determine a corresponding impedance of the device under test using an auto-balanced bridge technique. The measurement device includes a first terminal, a second terminal, a third terminal, and a fourth terminal. An end of a first transmission line is connected to the first terminal. Another end of the first transmission line is connected to a second terminal. An end of a second transmission line is connected to the third terminal. Another end of the second transmission line is connected to the fourth terminal. The measurement device measures a phase delay of the first transmission line and a phase delay of the second transmission line. An end of a third transmission line is connected to an end of the first transmission line. Another end of the third transmission line is connected to one of the first terminal and the second terminal. An end of a fourth transmission line is connected to an end of the second transmission line. Another end of the fourth transmission line is connected to one of the third terminal and the fourth terminal. The measurement device measures a combined phase delay of the connected first and third transmission lines and a combined phase delay of the connected second and fourth transmission lines. A difference between the combined phase delay of the connected first and third transmission lines and the phase delay of the first transmission line is calculated to determine a phase delay of the third transmission line. A difference between the combined phase delay of the connected second and fourth transmission lines and the phase delay of the second transmission line is calculated to determine a phase delay of the fourth transmission line. The corresponding impedance of the device under test is determined based on the phase delay of the third transmission line and the phase delay of the fourth transmission line.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic diagram of a circuit for measuring an impedance using an auto-balanced bridge technique;
FIG. 2 is a schematic diagram of a circuit for measuring an impedance using an auto-balanced bridge technique and cables connected thereto;
FIG. 3 is a schematic diagram of a circuit for measuring cable characteristics using an auto-balanced bridge technique and cables connected thereto; and
FIG. 4 is a schematic diagram of a circuit for measuring cable characteristics using an auto-balanced bridge technique and cables connected thereto.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to transmission line or cable length compensation in a measurement device and, in particular, to cable length compensation in a capacitance versus voltage (CV) analyzer that employs an auto-balanced bridge technique. The present invention will now be described with reference to the drawings, wherein like reference numerals are used to refer to like elements throughout. In the following description, for purposes of explanation, numerous specific details are set forth in order to provide a thorough understanding of the present invention. It may be evident, however, that the present invention can be practiced without these specific details. Additionally, other embodiments of the invention are possible and the invention is capable of being practiced and carried out in ways other than as described. The terminology and phraseology used in describing the invention is employed for the purpose of promoting an understanding of the invention and should not be taken as limiting.
The term “transmission line” refers to a conductive path between two points. Example transmission lines include coaxial cables, parallel two-wire, twisted pairs, strip lines, waveguides, and the like. Also included may be, for example, connectors and other devices included in the conductive path. Transmission line characteristics often become significant when the electrical length of the transmission line exceeds ¼ of the shortest wavelengths of the transmitted signal. If the transmission line characteristics, such as phase delay, become significant, it may be desirable to compensate for the electrical length of the transmission line when making impedance measurements on a DUT.
FIG. 1 provides a schematic diagram of a circuit 1 within a measurement device 2 for measuring the impedance of a DUT 4 . The measurement device 2 can be a CV analyzer that generates a test signal 6 having a frequency and determines the capacitance of the DUT 4 using an auto-balanced bridge technique.
The auto-balanced bridge technique will now be described. The test signal 6 , for example, a sine wave, is applied to the DUT 4 via a pathway that includes resistor R S 8 . Another signal 10 , for example, another sine wave, is applied via a pathway that includes resistor R I 12 . An auto-balance control circuit 14 monitors a voltage V 0 within the circuit 1 . The auto-balance control circuit 14 adjusts the amplitude and phase of signal 10 to maintain voltage V 0 at zero volts.
The measurement device 2 monitors a voltage V V at the output of a buffer 16 . The monitored voltage V V is a virtual version of voltage V 1 at the DUT 4 . With V 0 maintained at zero volts, the monitored voltage V V will equal the voltage across the DUT 4 .
It is to be appreciated that the electrical current I 1 that flows through the DUT 4 also flows the resistor R I 12 . Therefore, the current I 1 through the DUT 4 can be determined by measuring the voltage across the resistor R I 12 . The measurement device 2 monitors the voltage V I across the resistor R I 12 via an amplifier 18 . The current I 1 through the DUT 4 equals V I /R I .
The measurement device 2 can determine the impedance of the DUT 4 (Z DUT ) from the voltage V V across the DUT 4 and the current I 1 through the DUT 4 (e.g., V I /R I ). The impedance (e.g., capacitance) of the DUT 4 can be determined by the following equation: Z DUT =(V V /V I )·R I .
The DUT 4 is typically located remote from the measurement device 2 . As shown in FIG. 2 , cables A-D 21 , 22 , 23 , 24 connect the remote DUT 4 to the measurement device 2 . In an embodiment, cables A-D 21 - 24 are coaxial cables. The cables 21 - 24 can distort the DUT 4 impedance measurement, and the amount of distortion is dependent upon the length of the cables 21 - 24 . The cables 21 - 24 add phase delays “φ” to the circuit 1 a (φ=2πd/λ), where “d” is the electrical length of a cable and λ is the wavelength of an applied signal in vacuum. The distortion due to the phase delays added by the cables 21 - 24 can be corrected by the measurement device 2 if the phase delays of the cables are known.
It is possible that the phase delays of the cables are initially known. For example, some cables are manufactured to a target phase delay. If such cables are used to connect the DUT 4 to the measurement device 2 , then the measurement device 2 can be programmed to compensate for the known target phase delays when determining the impedance Z DUT of the DUT 4 .
It is also possible that the phase delays of the cables 21 - 24 are initially unknown. According to the present invention, the measurement device 2 can be configured to measure the phase delays of the cables 21 - 24 prior to determining the impedance Z DUT of the DUT 4 . The circuit 1 a with the DUT 4 removed is used to measure the phase delays of the cables 21 - 24 . With the DUT 4 removed, the circuit 1 a includes an open circuit portion between nodes 26 and 28 .
The measurement device includes terminals HC, HP, LP, and LC. Terminal HC is a “source” terminal, through which the test signal 6 is transmitted, and terminal HP is a corresponding “sense” terminal. Similarly, terminal LC is a source terminal for another signal 10 , and terminal LP is a corresponding sense terminal. One end of each cable 21 - 24 is connected to the measurement device 2 via terminals HC, HP, LP, and LC, respectively. Remote ends of cables A 21 and B 22 are connected at node 26 and remote ends of cables C 23 and D 24 are connected at node 28 .
The measurement device 2 transmits a signal, such as the test signal 6 , through terminal HC and along cable A 21 . The transmitted signal returns to the measurement device 2 along cable B 22 and through terminal HP, and the measurement device 2 determines a combined phase delay for cables A and B. The measurement device 2 also transmits a signal though terminal LC and along cable D 24 , which returns along cable C 23 and through terminal LP. The measurement device 2 determines a combined phase delay for cables C 23 and D 24 . Assuming that the individual phase delay of cable A 21 and the individual phase delay of cable B 22 are identical, the measurement device can calculate the individual phase delays of cables A and B by dividing the measured combined phase delay for cables A and B in half. Similarly, the individual phase delays of cables C 23 and D 24 can be calculated by dividing the measured combined phase delay for cables C and D in half. The cabling phase delays, whether combined or individual, are retained by the measurement device 2 within a memory (not shown). Further, measurement device 2 can determine and retain the electrical length of each cable A-D 21 - 24 .
After the cabling phase delays are determined, the DUT 4 is connected to the circuit 1 a at nodes 26 and 28 . The impedance of the DUT 4 is determined using the auto-balanced bridge technique while correcting for the cabling phase delays or electrical lengths.
Referring now to FIG. 3 and FIG. 4 , another example embodiment of a system for determining cabling phase delays is shown. Again, the DUT 4 is removed from the circuit 1 b when determining the cabling phase delays or electrical lengths.
As shown in FIG. 3 , cable X 30 is connected between terminals HC and HP and cable Y 32 is connected between terminals LP and LC. The measurement device 2 transmits a signal, such as the test signal 6 , through terminal HC and along cable X 30 . The transmitted signal returns to the measurement device 2 through terminal HP, and the measurement device 2 determines an individual phase delay for cable X 30 . The measurement device 2 also transmits a signal though terminal LC and along cable Y 32 , which returns through terminal LP. The measurement device 2 determines an individual phase delay for cable Y 32 .
As shown in FIG. 4 , one end of cable X 30 is disconnected from either terminal HC or HP, and cable A 21 or cable B 22 is installed between the end of cable X and the disconnected terminal. Similarly, one end of cable Y 32 is disconnected from either terminal LP or LC, and cable C 23 or cable D 24 is installed between the end of cable Y and the disconnected terminal. The measurement device 2 transmits a signal, such as the test signal 6 , through terminal HC and along cable X 30 and cable A 21 or B 22 . The transmitted signal returns to the measurement device 2 through terminal HP, and the measurement device 2 determines a combined phase delay for cable X 30 and cable A 21 or B 22 , whichever is connected. The measurement device 2 further determines the difference between the combined phase delay for cable X 30 and cable A 21 or B 22 and the individual phase delay for cable X, to determine the individual phase delay of cable A or B. The measurement device 2 also transmits a signal though terminal LC and along cable Y 32 and cable C 23 or D 24 , and the signal returns through terminal LP. The measurement device 2 determines a combined phase delay for cable Y 32 and cable C 23 or D 24 , whichever is connected. The measurement device 2 further determines the difference between the combined phase delay for cable Y 32 and cable C 23 or D 24 and the individual phase delay for cable Y, to determine the individual phase delay of cable C or D.
After the individual phase delay of each cable A-D 21 - 24 is determined, cables X 30 and Y 32 can be disconnected from the measurement device 2 . The DUT 4 is connected to the measurement device 2 through cables A-D 21 - 24 and between nodes 26 and 28 , as shown in FIG. 2 . The impedance of the DUT 4 is determined using the auto-balanced bridge technique while correcting for the cabling phase delays or electrical lengths.
It is to be appreciated that in determining the individual phase delay of each cable A-D 21 - 24 , the combined phase delay for cable X 30 and cable A 21 or B 22 can be determined prior to determining the individual phase delay for cable X 30 . Similarly, the combined phase delay for cable Y 32 and cable C 23 or D 24 can be determined prior to determining the individual phase delay for cable Y 32 . In this case, the set-up and measurements discussed above with respect to FIG. 4 occur prior to the set-up and measurements discussed above with respect to FIG. 3 . Further, cables X 30 and Y 32 can be chosen from among cables A-D 21 - 24 . For example, cable A 21 can be used as cable X 30 to determine the individual phase delay of cable B 22 and cable B can be used as cable X to determine the individual phase delay of cable A.
Cabling phase delays or electrical lengths, whether combined or individual, can be retained by the measurement device 2 within a memory (not shown), such as RAM or ROM.
It should be evident that this disclosure is by way of example and that various changes may be made by adding, modifying or eliminating details without departing from the fair scope of the teaching contained in this disclosure. The invention is therefore not limited to particular details of this disclosure except to the extent that the following claims are necessarily so limited. | A transmission line impedance compensation method includes the step of providing a measurement device that is adapted to source a test signal having a frequency to a device under test and to determine a corresponding impedance of the device under test using an auto-balanced bridge technique. A first transmission line, a second transmission line, a third transmission line, and a fourth transmission line are connected to said measurement device. An end of the first transmission line is connected to an end of second transmission line. An end of third transmission line is connected to an end of fourth transmission line. A combined phase delay of the connected first and second transmission lines, and a combined phase delay of the connected third and fourth transmission lines, are measured by the measuring device. The device under test is connected to the first transmission line, the second transmission line, the third transmission line, and the fourth transmission line after measuring the phase delays. The corresponding impedance of the device under test is determined based on both of the phase delays. | 6 |
Reference to related patents, the disclosure of which is hereby incorporated by reference:
U.S. Pat. No. 3,049,155
U.S. Pat. No. 3,618,640
U.S. Pat. No. 3,626,990
U.S. Pat. No. 3,749,135.
Reference to related disclosures, illustrating the state of the art: German Patent Disclosure Document DE-OS No. 33 46 030, Czechoslovakian Pat. No. 83,864, German Pat. No. 1,066,958, German Pat. No. 1,287,526.
Reference to related applications, the disclosure of which is hereby incorporated by reference, and assigned to the assignee of this application:
U.S. Ser. No. 07/123,376, filed Nov. 20, 1987, LINKA
U.S. Ser. No. 07/131,637, filed Dec. 11, 1987, LINKA et al
U.S. Ser. No. 07/163,619, filed Mar. 3, 1987, LINKA et al
U.S. Ser. No. 07/123,597, filed Nov. 20, 1987, LINKA.
The present invention relates to introducing and storing a weft thread of finite length in the storage compartment of a shuttle of a weaving loom by use of a compressed air jet, and more particularly to an arrangement and a method to so introduce a sharply defined air jet and, during introduction of the weft thread, relative movement between the air jet and the shuttle in a direction transverse to the air jet may occur.
BACKGROUND
Weaving looms in which a plurality of shuttles are moved through progressive sheds are well known; it is also known to introduce weft threads into continuously moving shuttles of a multi-feed or multi-system weaving loom by means of compressed air, introduced through an injector nozzle. A weft thread introduced through an injector nozzle sometimes will be placed in a weft thread storage area of the shuttle in the form of more or less ordered loops or other configurations. As the weft thread is pulled out of the storage area, the individual loops, which may be kinked, may pull against each other, hook against each other, or otherwise interfere with smooth pay-out, thus preventing orderly and proper placement of the weft thread into the shed of the fabric to be made. It has been proposed to form cross walls, located transverse to a central plane of the shuttle in order to subdivide the storage area into a plurality of communicating chambers. The shuttle is guided in a path past the air ejection nozzle of the weft thread injector, and the intention is a uniform distribution of the weft thread in separate loops, distributed in the respective chambers.
It has been found necessary to place the chambers spaced from each other; they cannot be made as small as would be desirable due to aerodynamic considerations; nor can they be placed as closely against each other as might be desirable. Thus, the shuttle will have a comparatively large overall length which cannot be decreased. This, however, is undesirable since the length of the shuttles decreases the number of sheds which can be formed, so that the speed of the weaving loom is decreased. If the shuttles are shorter, a larger number of shuttles can be accomodated in a given width of the warp threads. With shorter shuttles, and at the same operating speed of the shuttles, a larger number of weft threads can be introduced between the warp threads to more rapidly form fabric, so that the overall operating speed of the weaving loom is increased.
Sequentially located single chambers of shuttles of the prior art are open at their bottom, in order to permit the compressed air from the injector to be injected and then ejected without interference. The bottom opening, typically, is opposite the injector nozzles. Excessive lengths of weft thread, however, which may place themselves in the respective chambers must be prevented, however, from entering the opening in the bottom of the chamber. Such lengths, usually in the form of projecting loops, may catch on the shuttle path guide elements, or otherwise interfere with proper weaving. It has been proposed to form the bottom of the shuttle as a perforated region with comparatively small openings. This prevents weft threads from entering the openings but, on the other hand, is less effective since, if the openings are small enough to prevent the formation of weft thread loops, they have the tendency to become plugged by fluff or the like, even after some comparatively short operating time. In any event, they must be carefully cleaned at regular intervals which, of course, requires stopping of the weaving operation of the weaving loom.
THE INVENTION
It is an object to provide a method and a system carrying out the method to permit constructing shuttles in a more compact manner, by providing compact shuttle thread storage magazines or storage areas, in which the shuttles are so constructed that undesired collection of fluff or contaminants is avoided, while permitting excellent air flow and thus proper placement of weft thread in the storage area, without tendency to loop or hook into each other.
Briefly, the jet is guided into a pair of chambers located in a recess in the shuttle. The chambers are so positioned in the shuttle that they extend lengthwise of the shuttle adjacent each other, and separated from each other by a separating wall or the like extending along the longitudinal dimension, for example a longitudinal axis of the shuttle. The chambers are in communication with each other in the region of the bottom of the chambers, for example by an opening formed in the longitudinal wall. The air from the jet, thus, is guided essentially in a generally U-shaped path, from the top into one chamber, around the communicating portion of the wall, and out in reverse direction from the other chamber. The thread is separated from the jet in the chamber which is first exposed to the jet, to thereby define a thread storage chamber. It is located in the thread storage chamber in a zig-zag or meander-shaped path along the length of the storage chamber. The air from the jet is exhausted through the second chamber, deflected at the bottom of the separating wall by about 180°.
The separating wall preferably has laterally projecting bristles, plush fabric, elastic hairs or projections, closely spaced from each other secured thereto.
The air jet, preferably, is guided or directed through the region of bristles or hairs which are located at least in the thread storage chamber into which the thread is to be introduced. The air can pass through the gap forming the opening in the separating wall adjacent the bottom of the shuttle and out of the second chamber.
The arrangement has the advantage that no constriction or the like need be placed in the path of the air flow through the U-shaped shuttle recess. Rather, air injected by the injector can leave the second chamber throughout the length of the shuttle. Thus, the problem of stopping up of air ducts or plugging of air ducts or the like by collection of fluff is eliminated. The air jet which introduces the weft thread or pick in the first chamber blows through both chambers. It therefore causes continuous cleaning of the chambers, keeping them free from fluff, lint, and any other interfering contaminating deposits. The weaving process, that is, introduction of the pick, is not impeded, since the the pick is loaded into the shuttle outside of the shed. To prevent particles of fluff or lint from reaching the atmosphere, the shuttle, in accordance with a feature of the invention, may include fluff or lint filter material which is located in the second chamber, and which reliably prevents contamination of the air surrounding the weaving loom. Such a lint filter may be formed, for example, by further bristles located in the second chamber, or by an external filter.
The method and the new shuttle arrangement permit constructing shuttles of substantially shorter length than heretofore used for an equal length of weft thread, hence permits operation at a higher speed than previously possible; or, alternatively, the production of wider fabric in the same unit of time. It has been found that the weft thread which is ejected from the pneumatic ejector has a flutter movement, similar to a flag which is extended in the wind. Upon relative movement between the shuttle and the injector, which, typically, means a guidance of the shuttle rapidly in front of the injector nozzle, provides for continuous introduction of the weft thread in the first chamber in accordance with the respective relative speed of movement. Yet, the thread is introduced into the first chamber in zig-zag or meander shape at a speed which is substantially slower than the air speed of the jet. The thread is held against a wall of the storage chamber by the bristles or hairs on the opposite wall. The density of the placement of the bristles or hairs, as well as the respective length of the bristles or hair, and the construction of the shuttles themselves must be matched to the particular thread material which is to be used, considering the characteristics of the thread, e.g. thickness of thread, stiffness, or whether the weft thread is made of worsted yarn, carded, or has other and different surface characteristics.
Preferably, the bristles or hairs extend essentially over the entire width of the first chamber and, again preferably, are secured to the separating wall. The separating wall may be removably secured in the shuttle, so that separating walls with different bristles or hairs, of different lengths, heights, or bending characteristics, can be introduced into the shuttle as desired, so that respective characteristics of threads or yarn to be used can be readily matched to the appropriate bristle or hair characteristics while, also, permitting easy cleaning, if desired.
DRAWINGS
FIG. 1 is a schematic perspective view of a shuttle in accordance with the present invention;
FIG. 2 is a side view of the shuttle;
FIG. 3 is a top view of the shuttle;
FIG. 4 is a section along line IV--IV of FIG. 2; and
FIG. 5 is a side view of a separating wall element removed from the shuttle.
DETAILED DESCRIPTION
FIG. 1 illustrates a shuttle 1 into which a thread 31 cut to a predetermined length is to be injected by a pneumatic injector 2. The pneumatic injector 2 may be of any suitable construction, receiving compressed air in timed pulses as a thread 31 is introduced into the injector 2 and a shuttle passes in front of the injector. The injector is secured to a fixed portion of the weaving loom frame. The shuttle is moved in a predetermined path by a shuttle drive element or traveler 3. The traveler 3 and the shuttle 1 are magnetically coupled together, to permit passage of warp threads between the shuttle and the traveler when the shuttle enters the shed; this system is well known and reference may be made, for example, the referenced U.S. Pat. No. 3,626,990, by the inventor hereof, for a more detailed discussion.
The shuttle 1 is elongated; preferably, it is made of plastic material, and has magnetic inserts at a side facing the traveler 3 for magnetic coupling with the traveler 3. In longitudinal direction, it is shaped to form a narrow recess 4 (FIG. 4) of essentially U-shaped cross section. The recess 4 is defined by two parallel, flat and preferably smooth inner walls 5, 5', connected together by an essentially semicircularly curved smooth bottom wall 6. The wall at the end portion of the recess 4 in the shuttle is formed with grooves 7, 7'; into which a flat separating wall 8 is fitted. The separating wall 8 is sealed in the grooves, and so placed in the shuttle body that the lower edge of the separating wall 8 is spaced from the bottom wall 6 of the chamber to define a slit-like gap 10 at the base of the recess 4. The gap 10 extends throughout the length of the chamber 4, and subdivides the recess 4 into two adjacent chamber portions 11, 12. Chamber 11, also referred to as a chamber portion, forms a thread storage chamber, to store a pick. In the direction of air flow, it is the first chamber. The upper edge of the separating wall 8 is flush with the upper edge of the shuttle which, when under the injector (see FIG. 4) is close to the injector. The chamber 11 is defined by two side walls of similar height. The side wall 5' of the second chamber 12 has a lesser height than the height of the separating wall 8, so that the second chamber 12 is of lesser depth dimension than the chamber 11. The space between the separating wall 8 and the upper edge of the wall 5' leaves a wide opening 14, formed by the wall body portion 13 and the separating wall 8 and leading out of the second chamber portion 12. The end portion of the second chamber portion 12 forms an air exit opening to permit air used during injection of a thread to be ejected from the recess 4.
Elastic hairs or bristles 16 are secured to the separating wall 8, and extend into the first chamber portion 11 within a region 15. The hairs or bristles extend transversely to the longitudinal direction of the shuttle, that is, transversely to the separating wall 8. They are securely connected to the separating wall 8 and are closely located adjacent each other. The hairs or bristles 16 extend, essentially, over the entire width of the first chamber portion 11. The spacing of their ends from the smooth wall 5 of the shuttle body, as well as the thickness and density of the hairs or bristles 16 depend on the characteristics of the weft thread or weft yarn material to be stored within the shuttle.
The second chamber portion 12 also retains a region 17 with hairs or bristles, in which the hairs or bristles 18 are secured to the separating wall 8, extending in opposite direction, however, from the hairs or bristles 16. These hairs or bristles 18 terminate in a somewhat greater distance from the wall 5' of the body portion 13, which is smooth. Also, it is desirable to space the individual bristles or hairs 17 from each other so that the bristly or hairy region is less dense than the bristly or hairy region 15 in the first chamber portion 11. Both bristly or hairy regions 15, 17 extend over essentially the entire length of the recess 4 of the shuttle and along the major portion of the height of the separating wall where it is located within the respective chamber portion 11, 12, and preferably to the lower edge of the separating wall 8.
A thread brake 15 is located at the trailing end of the shuttle, located in a housing 20, 21 secured to or forming part of the rear wall of the shuttle body 1. A longitudinally extending wall portion 21, in alignment with the separating wall 8, carries a fixed brake surface, which is in operative association with a resiliently movable brake flap 22 (FIG. 2). Flap 22 can move transversely with respect to the longitudinal direction of the shuttle, by being pivotably secured in the shuttle body 1 by a pivot 23 (only seen in FIG. 2), so that it may pivot about an axis extending in the longitudinal direction of the shuttle. A spring 24 elastically engages the brake flap 22 against the brake surface on the wall extension 21. The upper end portion 25 of the flap 22, in cross section, is essentially T-shaped; the leg 26 of the T-shaped end facing the recess 4 forms an acute angle with the adjacent wall extension 21, as seen in FIG. 3 defining a ridge. The wall extension 21 is formed with a groove, or a depression, or a recess 27, in which the ridge of the bent or curved cross element of the T-shaped flap 22 can engage, see FIG. 3, in which the peak or ridge region thereof is received in the groove, depression, or recess 27. The T-shaped end portion of the brake flap 22 as shown engages in an opening 27 formed in the wall extension portion 21. The externally facing edge portions of the brake surface form retention regions for a weft thread in the shuttle. The retention regions, formed by surfaces of the T-shaped upper portion 25 of flap 22 and adjacent regions of the wall extension 21 are preferably slightly roughened, hardened, or coated with a wear-resistant coating material.
An operating element 28 for the brake 19 is located on the injector 2. This operating element is essentially wedge-shaped, as best seen in FIGS. 1 and 3. The leading edge 29 of the wedge-shaped operating element is directed towards the brake 19 and is so positioned and angled that the brake 19 can be opened as the shuttle passes beneath the injector for introduction of a pick, or weft thread or yarn therein by engaging against the angled leg 26 of the T-shaped end 25 and wedging it away from wall 21.
OPERATION
INSERTION OF A WEFT THREAD
The shuttle 1 is moved in the direction of the arrow 30 (FIG. 1) by being magnetically coupled to the traveler 3. As the shuttle passes the injector 2, secured to a fixed location, the nozzle-like end portion of the injector will enter the first chamber portion 11 up to and immediately adjacent the hairy or bristled region 15. The shuttle, at the leading edge, is formed with an introduction slot 310, extending in longitudinal direction and alignment with the first chamber portion 11 to the forward end of the shuttle (see FIG. 2), so that the injector 2 may freely enter into the first chamber portion 11 of the shuttle 1.
A thread supply apparatus, for example of the type described U.S. Ser. No. 07/163,619 of the cross-referenced patent applications by the inventor hereof, or of any other suitable type, provides a weft thread 31, or pick of suitable length. The weft thread element 31, upon being ejected from the injector nozzle 2, has a tendency to undulate or flutter. Consequently, it will be introduced in the storage region 4, and specifically in the first or storage chamber portion 11 of the shuttle 1 in essentially zig-zag or meander shape as schematically illustrated in FIG. 2 by the meander or zig-zag position of the stored thread 32. The stored thread 32 will be retained by the hairs or bristles in the region 15 of the first chamber portion 11, and the stored thread 32 can extend over the entire region 15 of the hairs or bristles 16. The bristles or hairs 16 which extend across the storage chamber 11 are positioned transversely to the direction of air as it is initially ejected in form of a jet, and also transverse to the relative movement of the shuttle 1 and injector 2. Air, however, can continue to flow through the gap adjacent the bottom wall 6, be deflected by the bottom wall of the chamber 4 by 180°, passed through the communicating gap 10 between the lower edge of the separating wall 8 and the bottom wall 6 of the chamber 4, and enter the second chamber portion 12. The air can then leave through the exit opening 14, unimpeded, throughout the length of the shuttle. Since the exit opening 14 of the second chamber portion 12 extends over the length of the side wall 13, the air being emitted from the exit opening 14 will leave with somewhat of a lateral direction. Any excess length of the weft thread which might occur is retained in the hairy or bristly region 17 of the second chamber 12, so it may not extend through the opening 14.
The shuttle continues to move in front of the injector 2. As the injector 2 reaches the trailing portion of the shuttle, the wedge-shaped edge 29 of the operating element 28 will enter the wedge-shaped gap between the wall extension 21 and the angled-off portion 26 of the T-shaped brake part 25. This causes the brake part or flap 25 to be laterally pivoted while, simultaneously, and as weft thread 31 continues to be fed through the injector, the now spaced brake surfaces can receive the weft thread therebetween. At the same time, the brake surfaces are cleaned by the air still being emitted from the injector 2.
The air supply to the injector 2 is timed. As soon as the shuttle 1 has passed the injector and has left the operating element 28, the brake flap 22 snaps against the housing wall extension 21 under pressure of the spring 24, so that the end portion 25 will fit against the housing wall 21 and resiliently clamp the end region of the pick 31, shown at 32, when stored in the shuttle elastically between the brake parts 25 and 21. The T-shaped end portion 25, then entering the opening 27, reliably prevents random release of the end of the pick or weft thread 31 from the brake 19.
Fluff, lint, and other contaminants cannot be blown by the air jet from the second chamber 12 into the surrounding atmosphere by placing, as shown in FIG. 4, an external shield filter 33. This filter is not strictly necessary, since the bristles or hairs 17 also retain fluff or lint. A suitable filter 33 is, for example, a gauze fabric, or similar air pervious lint filter material.
It may occur that the weaving loom, in which the method and the shuttle construction is to be used, is subject to sudden stopping, for example upon response of a "stop motion" device, or other safety apparatus. It has been found by experience that under such conditions the weft thread is not always properly introduced into the shuttle. It may then occur that the weft thead element actually introduced into the shuttle has excess length. Due to the U-shaped formation of the storage chamber for the weft thread, possibly occurring excess lengths will not have undesirable consequences since such excess lengths may merely be stored in the second chamber portion 12, and thus will not leave the shuttle, and thus be introduced into the shed and form an weaving error or defect. Placing the bristly region 17 into the second chamber has the advantage that such possible excess lengths of the weft thread will be reliably retained within the shuttle, rather than hanging out. The hairs or bristles in the region 17 of the second chamber 12 preferably terminate some slight distance before the opposite wall 5' of the chamber 12, and preferably have slightly lesser density, although, for some threads, the same density in the respective chamber portions 11 and 12 may be used.
The extent of the chambers into the shuttle body is preferably identical, which permits use of a single element 8 from which the bristles extend in opposite direction, the separating wall forming the separating element 8 then being inserted in the respective grooves 7, 7' (FIG. 3) of the shuttle body. The shuttle body itself can be symmetrical with respect to the upper edge, that is, it is not necessary to form the wall of the chamber portion 12 with a recess defining the exit opening 14. The two side walls of the shuttle body may have the same height. The recess or opening 14, however, is a preferred construction so that the height dimension of the respective chamber portions 11, 12 will be different. This preferred construction has the advantage that the shuttle is lighter, since less material is used, and will also save material. Additionally, the air ejection relationships are improved since the ejected air will be directed away from the shuttle path.
The application of bristles or hairs on the separating wall 8 in the first chamber portion 11 and, if used, also in the second chamber portion 12, is carried out in any well known and suitable manner. It has been found particularly economically desirable to apply the hairs or bristles by flock coating or dry coating of the separating wall. It is not absolutely necessary that the hairs or bristles extend from the separating wall to the wall surface 5, 5'. The bristles or hairs may also be applied to the shuttle body, if the shuttle body is made, for example, as a composite element. For ease of manufacture, placing the hairs or bristles on the separating wall 8 is preferred. Flock coating of the wall portions 5, 5' is also possible.
The injector 2 preferably cooperates with the shuttle 1 such that it engages within the first chamber portion 11. This reliably eliminates malfunction by confining the air jet from the nozzle of the injector, and prevents unintended deflection of the air jet by a shuttle element.
The thread brake 19 contributes to orderly insertion of the weft thread into the shed of the loom. An elastic friction brake, as described, is particularly suitable. This arrangement also permits easy coordination with the injector 2 by so constructing the friction brake that it is automatically opened by the wedge edge 29, so that the injector itself will form the brake opening element to permit placement of the weft thread in the brake for subsequent clamping therein. The arrangement permits locating the end portion of the injected weft thread close to the trailing end of the shuttle after the insertion. Opening a brake to receive the weft thread is automatic and occurs without further apparatus upon relative movement between the injector and the shuttle. Synchronization, likewise, of movement is automatic. The air jet, being emitted from the nozzle of the injector, cleans the brake surfaces, so that no fluff or lint can deposit thereon.
The arrangement in which a fixed brake surface is located on the shuttle, for cooperation with the movable T-shaped element 22, is particularly simple since only one brake surface has to be movably positioned on the shuttle. Coating the respective braking surfaces with wear-resistant material is particularly desirable if weft threads or yarn are used which are made of man-made material, such as synthetics of various types. The weft thread, upon introduction into the shed, is retained in the brake by the simple retention element of a groove or notch 27, over which the cross element 26 of the T-shaped brake element can engage, the cross element being angled or offset to form a ridge or peak which can engage in the groove or notch 27.
Practical experience has shown that even long weft thread elements can be stored within a short storage region of a shuttle. Tangling of the weft thread, or entangling of elements thereof, for example due to kinking or bunching of weft thread portions, is essentially eliminated. All conditions for reliable weaving and introduction of the weft thread into the shed are therefore obtained.
The invention is applicable for various types of weaving looms, and particularly suitable for weaving looms with continuous movement of the shuttle, for example for back-to-back linear weaving looms with a continuous closed shuttle path, circular weaving looms or the like.
Various changes and modifications may be made within the scope of the inventive concept. | To introduce weft threads (31) or picks of finite length into a storage shuttle (1), the shuttle is formed with a longitudinal recess (4) which is divided into two chambers (11, 12) by a longitudinally extending separating wall (8) leaving a gap (10) between the bottom edge of the separating wall and the bottom wall (6) of the recess (4). Bristles or hairs extend preferably from both sides of the separating wall (8) towards the opposite wall (5, 5') defining the recess (4). A weft thread injector (2) is positioned to engage into the first chamber (11) to pneumatically inject the weft thread into the first chamber, to be retained in undulating or zig-zag pattern in the first chamber. Air is deflected by 180° around the gap (10) and exhausted at an exhaust opening (14) leading from the second chamber (12). Preferably, a thread brake (19) is located at the trailing end of the shuttle, in the direction of relative movement between the shuttle and the injector to clamp the end of the injected weft thread. | 3 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a process for the arylation of olefins by reaction of haloaromatics or arylsulfonates with olefins in the presence of a palladium catalyst and a bulky nitrogen base, if appropriate in a dipolar aprotic solvent.
2. Background of the Invention
Many aryl olefins have great industrial importance as fine chemicals, UV absorbers, starting materials for polymers and intermediates for active compounds.
The preparation of arylolefins is frequently carried out by means of palladium-catalyzed coupling of iodoaromatics or bromoaromatics, and to a lesser extent chloroaromatics or arylsulfonates, with olefins. Owing to the high price of iodoaromatics and bromoaromatics and the large amounts of waste product caused by the high molar masses, their use on an industrial scale is disadvantageous. However, the more readily available and therefore more attractive chloroaromatics have a comparatively low reactivity.
Littke and Fu (J. Am. Chem. Soc. 2001, 123, 6989) describe a process in which chloroaromatics are reacted with olefins at room temperature using palladium-dibenzylideneacetone ([Pd 2 (dba) 3 ]) and tri-tert-butylphosphine in the presence of dicyclohexylmethylamine in dioxane. However, the turnover numbers (TONs) are low and large amounts of palladium catalyst are required for the process described, which makes its industrial application uneconomical.
There was therefore a need to develop a process which makes it possible for haloaromatics, in particular chloroaromatics, to be coupled with olefins in an efficient way.
SUMMARY OF THE INVENTION
We have now found a process for preparing arylolefins, which is characterized in that
aromatic compounds of the general formula (I),
Ar—[X] n (I),
where
n is one or two and Ar is a substituted or unsubstituted aromatic radical and X are each, independently of one another, chlorine, bromine, iodine or a sulphonate, are reacted with olefins which bear at least one hydrogen atom on the double bond in the presence of a palladium catalyst, at least one bulky nitrogen base and in the presence of a dipolar aprotic solvent.
DETAILED DESCRIPTION OF THE INVENTION
It may be pointed out at this juncture that any combinations of preferred ranges are encompassed by the invention.
For the purposes of the invention, Ar is, by way of example and preferably, a carbocyclic aromatic radical having from 6 to 24 framework carbon atoms or a heteroaromatic radical having from 5 to 24 framework carbon atoms in which no, one, two or three framework carbon atom(s) per ring, but at least one framework carbon atom in the total molecule, can be replaced by heteroatoms selected from the group consisting of nitrogen, sulphur and oxygen. Furthermore, the carbocyclic aromatic radicals or heteroaromatic radicals may be substituted by up to five identical or different substituents per ring selected from the group consisting of hydroxy, fluorine, nitro, cyano, free or protected formyl, C 1 -C 12 -alkyl, C 5 -C 14 -aryl, C 6 -C 15 -arylalkyl, —PO—[(C 1 -C 8 )-alkyl] 2 , —PO—[(C 5 -C 14 )-aryl] 2 , —PO—[(C 1 -C 8 )-alkyl)(C 5 -C 14 )-aryl)], tri(C 1 -C 8 -alkyl)siloxyl and radicals of the general formula (II),
A—B—D—E (II)
where, independently of one another,
A is absent or is a C 1 -C 8 -alkylene radical and B is absent or is oxygen, sulphur or NR 1 ,
where R 1 is hydrogen, C 1 -C 8 -alkyl, C 6 -C 15 -arylalkyl or C 5 -C 14 -aryl and
D is a carbonyl group and E is R 2 , OR 2 , NHR 3 or N(R 3 ) 2 ,
where R 2 is C 1 -C 8 -alkyl, C 6 -C 15 -arylalkyl, C 1 -C 8 -haloalkyl or C 5 -C 14 -aryl and R 3 are each, independently of one another, C 1 -C 8 -alkyl, C 6 -C 15 -arylalkyl or C 6 -C 14 -aryl or the moiety N(R 3 )2 is a cyclic amino radical,
and radicals of the general formulae (IIIa-e)
A—E (IIIa)
A—SO 2 —E (IIIb)
A—B—SO 2 R 2 (IIIc)
A—SO 3 W (IIId)
A—COW (IIIe)
where A, B, E and R 2 are as defined above and W is OH, NH 2 , or OM, where M can be an alkali metal ion, half an equivalent of an alkaline earth metal ion, an ammonium ion or an organic ammonium ion.
For the purposes of the invention, alkyl or alkylene or alkoxy are each, independently of one another, a straight-chain, cyclic, branched or unbranched alkyl or alkylene or alkoxy radical which may be further substituted by C 1 -C 4 -alkoxy radicals. The same applies to the alkyl part of an arylalkyl radical.
In all contexts, C 1 -C 6 -alkyl is preferably methyl, ethyl, n-propyl, isopropyl, n-butyl, tert-butyl, n-pentyl, cyclohexyl or n-hexyl, C 1 -C 8 -alkyl may also be, for example, n-heptyl, n-octyl or isooctyl, C 1 -C 12 -alkyl may also be, for example, n-decyl and n-dodecyl and C 1 -C 20 -alkyl may also be n-hexadecyl and n-octadecyl.
In all contexts, C 1 -C 4 -alkylene is preferably methylene, 1,1-ethylene, 1,2-ethylene, 1,1-propylene, 1,2-propylene, 1,3-propylene, 1,1-butylene, 1,2-butylene, 2,3-butylene and 1,4-butylene, C 1 -C 8 -alkylene may also be 1,5-pentylene, 1,6-hexylene, 1,1-cyclohexylene, 1,4-cyclohexylene, 1,2-cyclohexylene and 1,8-octylene.
In all contexts, C 1 -C 4 -alkoxy is preferably methoxy, ethoxy, isopropoxy, n-propoxy, n-butoxy and tert-butoxy, C 1 -C 8 -alkoxy may also be cyclohexyloxy.
The general designation aryl as substituent encompasses carbocyclic radicals and heteroaromatic radicals in which no, one, two or three framework atoms per ring, but at least one framework atom in the overall radical, are heteroatoms selected from the group consisting of nitrogen, sulphur and oxygen. C 5 -C 10 -aryl is, by way of example and preferably, phenyl, pyridyl, o-, m-, or p-tolyl, C 5 -C 14 -aryl may also be anthracenyl.
The same applies to the aryl part of an arylalkyl radical. C 6 -C 15 -arylalkyl is, by way of example and preferably, benzyl.
For the purposes of the invention, haloalkyl and fluoroalkyl are each, independently of one another, a straight-chain, cyclic, branched or unbranched alkyl radical which may be monosubstituted, polysubstituted or fully substituted by halogen atoms selected independently from the group consisting of fluorine, chlorine and bromine or by fluorine.
In all contexts, C 1 -C 8 -haloalkyl is, by way of example and preferably, trifluoromethyl, trichloromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl or nonafluorobutyl, C 1 -C 8 -fluoroalkyl may be trifluoromethyl, 2,2,2-trifluoroethyl, pentafluoroethyl or nonafluorobutyl.
Protected formyl is a formyl radical which has been protected by conversion into an aminal, acetal or a mixed aminal-acetal, with the aminals, acetals and mixed aminal-acetals being able to be acyclic or cyclic.
Protected formyl is, by way of example and preferably, a 1,1-(2,5-dioxy)cyclopentylene radical.
In the process of the invention, preference is given to using aromatic compounds of the general formula (I) in which
n=one and Ar is a substituted or unsubstituted aromatic radical selected from the group consisting of phenyl, naphthyl, biphenyl, binaphthyl, phenanthrenyl, anthracenyl, fluorenyl, pyridinyl, oxazolyl, thiophenyl, benzofuranyl, benzothiophenyl, dibenzofuranyl, dibenzothiophenyl, furanyl, indolyl, pyridazinyl, pyrazinyl, pyrimidinyl, triazolyl and quinolinyl which may also be further substituted by no, one, two or three radicals per ring which are selected independently from the group consisting of fluorine, nitro, cyano, di(C 1 -C 6 -alkyl)amino, formyl, C 1 -C 6 -alkyl, C 5 -C 10 -aryl, C 1 -C 8 -fluoroalkyl, C 1 -C 8 -fluoroalkoxy, C 1 -C 8 -alkoxy, CO(C 1 -C 4 -alkyl), COO—(C 1 -C 6 )-alkyl, —CON(C 1 -C 6 -alkyl) 2 , and X is chlorine, bromine, iodine, C 1 -C 8 -perfluoroalkylsulphonyloxy such as trifluoromethanesulphonyloxy or nonafluorobutanesulphonyloxy or benzenesulphonyloxy or tolylsulphonyloxy.
In the process of the invention, particular preference is given to using aromatic compounds of the general formula (I) in which
n=one and Ar is a phenyl radical which may be further substituted by no, one, two or three radicals selected independently from the group consisting of fluorine, cyano, C 1 -C 4 -alkyl, formyl, trifluoromethyl, trifluoromethoxy, acetyl, COO—(C 1 -C 6 )-alkyl, —CON(C 1 -C 6 -alkyl) 2 and X is chlorine or bromine.
Very particular preference is given to using 4-chlorobenzotrifluoride
Palladium catalysts used are, by way of example and preferably, palladium complexes.
Palladium complexes can, for example, be generated from palladium compounds and suitable ligands in the reaction solution, or can be used in the form of previously isolated palladium complexes.
Isolated palladium complexes suitable for the process of the invention are, for example, palladium complexes containing phosphorus compounds such as phosphines, phosphites, phosphonites or mixtures thereof, preferably phosphines, as ligands.
As palladium complexes which can contain phosphorus compounds as ligands, use is made, by way of example and preferably, of complexes of the general formula (IV),
[PdL 2 An 2 ] (IV)
where
L is in each case a monophosphorus compound or L 2 together represents a diphosphorus compound and An is an anion, preferably chloride, bromide, iodide, acetate, propionate, allyl or cyclopentadienyl, or complexes of the general formula (IVb)
[PdL n ] (IVb)
where n is 2, 3 or 4 and
L is in each case a monophosphorus compound or can represent half an equivalent of a diphosphorus compound.
Monophosphorus compounds are, by way of example and preferably, compounds of the general formula (Va)
P(E—R 4 ) 3 (Va)
where
E are each, independently of one another and independently of R 4 , absent or oxygen and the radicals R 4 are each, independently of one another, C 1 -C 8 -alkyl or unsubstituted phenyl, naphthyl or ferrocenyl or phenyl, naphthyl or ferrocenyl substituted by one, two or three radicals R 5 , where
R 5 is C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, chlorine, fluorine, N(C 1 -C 6 -alkyl) 2 , CO 2 —(C 1 -C 6 -alkyl), —CON(C 1 -C 6 -alkyl) 2 , cyano or CO(C 1 -C 6 -alkyl).
Particularly preferred monophosphorus compounds are those of the general formula (Va) in which E is absent and R 4 are each, independently of one another, C 1 -C 8 -alkyl or unsubstituted phenyl or naphthyl or ferrocenyl or phenyl or naphthyl or ferrocenyl substituted by one, two or three radicals R 5 , where
R 5 is C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, chlorine or fluorine.
Very particular preference is given to monophosphorus compounds of the general formula (Va) in which E is absent
and two or three of the radicals R 4 are each, independently of one another, C 1 -C 8 -alkyl and no or one radical R 4 is unsubstituted phenyl or naphthyl or phenyl or naphthyl substituted by one, two or three radicals R 5 , where R 5 is C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, chlorine or fluorine.
Even more preferred monophosphorus compounds are tri(tert-butyl)phosphine, phenyldi(tert-butyl)phosphine and ferrocenyldi(tert-butyl)phosphine.
Diphosphorus compounds can be, by way of example and preferably, compounds of the general formula (Vb),
(R 6 —E) 2 P—E—Z—E—P(E—R 6 ) 2 (Vb)
where
E are each, independently of one another and independently of R 6 and Z, absent or oxygen and
the radicals R 6 are each, independently of one another, C 1 -C 8 -alkyl or phenyl, naphthyl or heteroaryl having from 5 to 12 framework carbon atoms which may be unsubstituted or substituted by one, two or three radicals R 7 , where R 7 are selected independently from the group consisting of C 1 -C 8 -alkyl, C 1 -C 8 -alkoxy, fluorine and cyano and
Z is an unsubstituted or substituted radical selected from the group consisting of C 1 -C 4 -alkylene, 1,2-phenylene, 1,3-phenylene, 1,2-cyclohexyl, 1,1′-ferrocenyl, 1,2-ferrocenyl, 2,2′-(1,1′-binaphthyl) and 1,1′-biphenyl.
Preference is given to using complexes which contain monophosphorus compounds as ligands.
Preferred isolated palladium complexes are bistriphenylphosphinepalladium(II) dichloride, tetrakistriphenylphosphinepalladium(0), bistri-o-tolylphosphinepalladium(0), tricyclohexylphosphinepalladium(0)-diallyl ether complex, bistricyclohexylphosphinepalladium(0).
In the process of the invention, palladium complexes generated in the reaction solution from palladium compounds and ligands are preferred as palladium catalysts.
As palladium compounds, it is possible to use, by way of example and preferably, Pd 2 (dibenzylideneacetone) 3 or allylpalladium chloride or bromide or compounds of the general formula (VIa),
Pd(Y 1 ) 2 (VIa)
where
y 1 is an anion, preferably chloride, bromide, acetate, propionate, nitrate, methanesulphonate, trifluoromethanesulphonate, acetylacetonate, allyl or cyclopentadienyl,
or palladium compounds of the general formula (VIb)
Pd(Y 2 ) 2 L 2 (VIb)
where
y 2 is an anion, preferably chloride, bromide, acetate, methanesulphonate or trifluoromethanesulphonate, nonafluorobutanesulphonate, tetrafluoroborate or hexafluorophosphate and L are each a nitrile, preferably acetonitrile, benzonitrile or benzyl nitrile, or an olefin, preferably cyclohexene or cyclooctene, or L 2 together represents a diolefin, preferably norbornadiene or 1,5-cyclooctadiene,
or palladium compounds of the general formula (VIc)
M 2 [Pd(Y 3 ) 4 ] (VIc),
where
Y 3 is a halide, preferably chloride or bromide, and M is lithium, sodium, potassium, ammonium or organic ammonium.
Preferred palladium compounds are palladium(II) acetate, palladium(II) chloride, palladium(II) bromide, palladium(II) propionate, palladium(II) acetylacetonate, lithium, sodium or potassium tetrachloropalladate, bisbenzonitrilepalladium(II) chloride, bisacetonitrilepalladium(II) chloride, cyclopentadienyl(allyl)palladium(II), and palladiumdibenzylideneacetone complexes such as [Pd 2 (dba) 3 ].
Preference is given to using the phosphorus compounds of the general formulae (Va) and (Vb) as ligands for the generation of palladium complexes in the reaction solution, with monophosphorus compounds of the general formula (Va) being particularly preferred. The above-mentioned preferred ranges apply in the same way.
The molar ratio of phosphorus to palladium in the reaction mixture can be, for example, from 1:1 to 100:1, preferably from 2:1 to 15:1, particularly preferably from 2:1 to 10:1.
In the process of the invention, the molar ratio of X to be replaced in compounds of the general formula (I) to palladium can be, for example, from 10 to 20 000; preference is given to a ratio of from 100 to 5 000, very particularly preferably from 500 to 2 000.
The process of the invention is carried out in the presence of at least one, preferably one, bulky nitrogen base.
Bulky nitrogen bases are, for example, amines of the general formula
NR 8 R 9 R 10 (VII)
where R 8 , R 9 and R 10 are each, independently of one another, C 1 -C 20 -alkyl, C 5 -C 14 -aryl or C 6 -C 15 -arylalkyl or two or three of the radicals R 8 , R 9 and R 10 together with the nitrogen atom may form a monocyclic, bicyclic or tricyclic heterocycle having from 4 to 8 carbon atoms per ring,
with the proviso that one, two or three of the radicals R 8 , R 9 and R 10 , preferably two or three, are each, independently of one another, either bound to the nitrogen atom via a tertiary or quaternary Sp 3 carbon atom or are an aryl radical which is monosubstituted or disubstituted, preferably disubstituted, in the ortho positions.
Radicals which may be bound to the nitrogen atom via a tertiary or quaternary Sp 3 carbon atom are, by way of example and preferably, isopropyl, isobutyl, tert-butyl, 1-methylbutyl, 1-ethylpropyl, 1,1-dimethylpropyl, 1,2-dimethylpropyl, 1-methylpentyl, 1,1-dimethylbutyl, 1,2-dimethylbutyl, 1,3-dimethylbutyl, 1-ethylbutyl, 1,1,2-trimethylpropyl, 1,2,2-trimethylpropyl, 1-ethyl-1-methylpropyl, cyclopentyl, cyclohexyl and cycloheptyl.
Aryl radicals which are monosubstituted or disubstituted in the ortho positions are, for example, o-tolyl, 2,6-dimethylphenyl, 2-ethyl-6-methylphenyl, 2,6-diisopropylphenyl, o-anisyl and 2,6-dimethoxyphenyl.
For the purposes of the invention, monocyclic heterocycles are, for example, N-methyl-2,2,6,6-tetramethylpiperidine and N-methyl-2,5-dimethylpyrrolidine.
Further bulky nitrogen bases are N-heteroaromatic compounds which are substituted in both the ortho positions relative to the nitrogen.
These are preferably 2,6-disubstituted pyridines such as 2,6-lutidine, 2,6-diethylpyridine, 2,6-diisopropylpyridine, 2,6-dimethoxypyridine, 2,6-di-tert-butylpyridine.
In the process of the invention, bulky nitrogen bases used are very particularly preferably ethyldiisopropylamine, triisopropylamine, diisopropylaniline, triisobutylamine, ethyldiisobutylamine, dicyclohexylmethylamine, dicyclohexylethylamine, cyclohexyldiethylamine, cyclohexyldimethylamine and 2,6-bis-diisopropylpyridine, among which dicyclohexylmethylamine, dicyclohexylethylamine, cyclohexyldimethylamine, cyclohexyldimethylamine are very particularly preferred.
The molar amount of base used can be, for example, from 0.5 to 100 times, preferably from 1.0 to 10 times, particularly preferably from 1.0 to 1.5 times and very particularly preferably from 1.0 to 1.2 times, the molar amount of X to be replaced in the general formula (I).
In an embodiment of the process of the invention, the bulky nitrogen base can be used in combination with another base. In this case, for example, from 1 to 95% of the amount of bulky nitrogen base can be replaced by a nonbulky nitrogen base.
Nonbulky nitrogen bases for the purposes of the invention are, for example, alkali metal and alkaline earth metal carboxylates such as acetates, propionates, benzoates, alkali metal and alkaline earth metal carbonates, hydrogencarbonates, phosphates, hydrogenphosphates, hydroxides. Alkali metals are preferably lithium, sodium, potassium and caesium, alkaline earth metals are preferably calcium, magnesium and barium.
As olefins which bear at least one hydrogen atom on the double bond, it is possible to use, for example, those of the general formula (VIII),
R 11 CH═C 12 R 13 (VII)
where, independently of one another,
R 11 is hydrogen or methyl and R 12 is hydrogen or methyl and R 13 can be hydrogen, cyano, SO 3 M, C 1 -C 8 -alkyl, a carbocyclic aromatic radical having from 6 to 18 framework carbon atoms or a heteroaromatic radical having from 5 to 18 framework carbon atoms in which no, one, two or three framework carbon atoms per ring, but at least one framework carbon atom in the total molecule, may be replaced by heteroatoms selected from the group consisting of nitrogen, sulphur and oxygen
or a radical of the general formula (IX)
where
G is OM, OH, NH 2 , OR 14 , NHR 14 or N(R 14 ) 2 , and R 14 is C 1 -C 12 -alkyl, C 6 -C 15 -arylalkyl or C 5 -C 14 -aryl or
the N(R 14 ) 2 moiety is a cyclic amino radical such as morpholino, pyrrolidino or piperidino, and M can be an alkali metal ion, half an equivalent of an alkaline earth metal ion, an ammonium ion or an organic ammonium ion.
The carbocyclic aromatic radicals and heteroaromatic radicals can be substituted in the same way as described under the aromatic compounds of the general formula (I).
Preferred examples of olefins of the general formula (X) are ethene, propene, butene, 1,1,1-trifluoro-2-propene, substituted or unsubstituted vinyl-C 6 -C 10 -aromatics such as styrene or the isomeric vinylnaphthalenes, 2-, 3- or 4-fluorostyrene, 2-, 3- or 4-chlorostyrene, 2-, 3- or 4-bromostyrene, 2-, 3- or 4-iodostyrene, 2-, 3- or 4-cyanostyrene, 2-, 3- or 4-(C 1 -C 12 )-alkoxystyrene such as 2-, 3- or 4-methoxystyrene, 2-, 3- or 4-nitrostyrene, 2-, 3- or 4-styrenecarboxylic acid, C 1 -C 12 -alkyl 2-, 3- or 4-styrenecarboxylates such as methyl 2-, 3- or 4-styrenecarboxylate, C 6 -C 12 -aryl 2-, 3- or 4-styrenecarboxylates such as phenyl 2-, 3- or 4-styrenecarboxylate, 2-, 3- or 4-styrenesulphonic acid or their salts, 3- or 4-vinylphthalic acid, di-C 1 -C 12 -alkyl 3- or 4-vinylphthalates such as dimethyl 3- or 4-vinylphthalate, di-C 6 -C 10 -aryl 3- or 4-vinylphthalates such as diphenyl 3- or 4-vinylphthalate, 3- or 4-vinylphthalic anhydride, vinylhetaryls such as N-vinylimidazole or 2- or 4-vinylpyridine, also acrylonitrile, acrylic acid, C 1 -C 12 -alkyl acrylates such as methyl acrylate, ethyl acrylate, n-propyl acrylate, 2-ethylhexyl acrylate, acrylamide, vinylsulphonic acid and its sulphonates and acrylamide.
As olefins having at least one hydrogen substituent, very particular preference is given to ethylene, propene, acrylonitrile, acrylic acid, methyl acrylate, 2-ethylhexyl acrylate, acrylamide, 1,1,1-trifluoro-2-propene and styrene, with especial preference being given to acrylonitrile, methyl acrylate, acrylamide and styrene and greatest preference being given to acrylamide.
The amount of olefin used can be, for example, from 0.2 to 200 times (when used as solvent) the molar amount of the aromatic compound of the general formula (I); from 0.5 to 5 times is preferred and from 0.8 to 1.2 times is very particularly preferred. Even greater preference is given to 0.9 to 1.0 times.
If aromatic compounds of the general formula (I) or olefins of the general formula (VIII) which bear a free acid group such as a sulphonic acid or carboxylic acid group, the amount of base used, viz. a bulky nitrogen base or nonbulky nitrogen base, has to be increased correspondingly.
The process of the invention is carried out in the presence of a dipolar aprotic solvent.
Preferred dipolar aprotic solvents are amide solvents such as dimethylformamide, dimethylacetamide, N-methylpyrrolidone or N-methylcaprolactam;
sulphoxides and sulphones such as dimethyl sulphoxide or tetramethylene sulphone (sulpholane) or mixtures of such solvents; nitriles such as acetonitrile, benzonitrile and benzyl nitrile, ketones such as dimethyl ketone, diethyl ketone, methyl tert-butyl ketone.
Dimethylformamide, dimethylacetamide and N-methylpyrrolidone are particularly preferred.
Dimethylacetamide is very particularly preferred.
The amount of any solvent used can be, for example, from 50 ml to 5000 ml, preferably from 100 to 500 ml, per mol of the aromatic compound of the general formula (I).
The reaction temperature can be, for example, from 20° C. to 200° C., preferably from 80 to 150° C. and particularly preferably from 0° C. to 120° C.
The reaction can be carried out at, for example, from 0.2 to 100 bar; preference is given to atmospheric pressure.
The reaction time can be, for example, from 0.2 hour to 72 hours; preference is given to from 1 to 36 hours.
The reaction is preferably carried out under a protective gas atmosphere with substantial exclusion of oxygen and moisture. Possible protected gases are, for example, nitrogen and noble gases such as argon or mixtures of such gases.
In a preferred embodiment of the process of the invention, the aromatic compound of the general formula (I) together with the olefin, the base, the palladium compound and the ligand are placed in a reaction vessel under protective gas and the mixture is heated to the reaction temperature while stirring. After the reaction is complete, the mixture is poured into water. Solid products then precipitate and can be filtered off with suction and, for example, washed with water. Liquid products can be extracted by means of an organic solvent which is immiscible or sparingly miscible with water and be worked up, for example, by distillation.
Solid products can, if appropriate, be purified further by, for example, recrystallization or reprecipitation.
As an alternative, it is also possible for the aromatic compound of the general formula (I) together with the olefin, the base and the ligand to be placed in a reaction vessel and the palladium compound to be added.
Furthermore, it is also possible for the aromatic compound of the general formula (I) together with the base, the ligand and the palladium compound to be placed in a reaction vessel and the olefin to be added.
Furthermore, it is also possible for the olefin together with the base, the ligand and the palladium compound to be placed in a reaction vessel and the aromatic compound of the general formula (I) to be added.
Furthermore, it is also possible for the base, the ligand and the aromatic compound of the general formula (I) to be placed in a reaction vessel and the palladium compound to be added.
In each of the possible methods of addition mentioned above, the ligand can also be added together with the palladium compound.
It is advantageous to use a weakly acidic aqueous solution during the work-up to bind any remaining base as salt. The base can, for example, be recovered by alkalisation and extraction of the washing liquid with an organic solvent.
The process of the invention gives arylolefins of the general formula (X)
Ar—(R 11 C═CR 12 R 13 ) n (X)
where
Ar and n are as defined under the general formula (I) and R 11 , R 12 , R 13 are as defined under the general formula (VIII).
The process of the invention is particularly useful for preparing arylacrylic acid derivatives of the general formula (XI)
Ar—(R 11 ═R 12 R 13 ) (XI)
where
Ar is as defined under the general formula (I) and R 11 , R 12 are as defined under the general formula (X) and R 13 is cyano or a radical of the general formula (XI) with the meanings specified there.
The advantages of the process of the invention are the ease with which it can be carried out and the high yields of aromatic olefins. Furthermore, high catalyst turnover numbers (TONs) of far above 100 mol of haloaromatic/mol of palladium catalyst are achieved.
The invention is further illustrated but is not intended to be limited by the following examples in which all parts and percentages are by weight unless otherwise specified.
EXAMPLES
Examples 1-9
0.4 ml of 4-chlorobenzotrifluoride, 0.178 g of acrylamide, 1.4 mg (0.24 mol %) of palladium acetate and 4.8 mg of phenyldi(t-butyl)-phosphine and 2 ml of dimethylacetamide are placed in a Schlenk vessel. The indicated amount of the specified base is in each case added to this initial charge and the mixture is heated to 130° C. under protective gas. After 4 hours, samples are taken and analysed by HPLC.
Weight
Example
used
Yield
number
Base
[g]
[%]
1 (comparison)
Na 2 CO 3
0.382
0
2 (comparison)
Triethylamine
0.364
6.4
3 (comparison)
Diazabicyclooctane
0.404
15.4
4 (comparison)
Diazabicycloundecane
0.548
0
5
Ethyldiisopropylamine
0.465
35.4
6
Dicyclohexylmethylamine
0.703
>99
7
Dicyclohexylethylamine
0.754
83
8
Cyclohexyldiethylamine
0.559
>99
9
Cyclohexyldimethylamine
0.458
>99
Example 10
0.40 ml of 4-chlorobenzotrifluoride, 0.178 g of acrylamide, 0.7 mg of palladium acetate (0.12 mol %), 2.7 mg of di(tert-butyl)phenylphosphine and 3 ml of dimethylacetamide are placed in a Schlenk vessel. 0.559 g of cyclohexyldiethylamine is added to this initial charge, and the mixture is then heated to 120° C. under protective gas. After 5.5 hours, a sample is taken and analysed by HPLC. 84% conversion to the desired product (TON=700, TOF=127 h −1 ).
Examples 11 and 12
In each case in a Schlenk vessel, 237.6 mg of acrylamide, 0.50 ml of 4-chlorobenzotrifluoride, 0.87 ml of dicyclohexylmethylamine, 4.2 mg of palladium acetate, 16.5 mg of di(tert-butyl)phenylphosphine and 100 mg of 1,3,5-trimethoxybenzene as internal standard are dissolved once in 3 ml of dimethylacetamide (Example 11) and once in 3 ml of dioxane (Example 12). The vessels are then placed in the same oil bath at 100° C. and samples for HPLC are taken at regular intervals. The results were used to produce a time-conversion table.
Conversion in
Conversion in
%
%
Time [h]
(Example 11)
(Example 12)
0
0
0
0.5
1.3
2.3
1
8.3
3.7
1.5
11.4
5.8
2
15.2
8.4
2.5
20.2
8.4
4
30.1
14.5
Time-conversion table comparing the solvents dimethylacetamide (Example 11) and 1,4-dioxane (Example 12).
Examples 13 and 14
In each case in a Schlenk vessel, 237.6 mg of acrylamide, 0.50 ml (3.71 mmol) of 4-chlorobenzotrifluoride, 0.87 ml of dicyclohexylmethylamine, 0.8 mg (0.11 mol %) of palladium acetate, 3.3 mg of di(tert-butyl)phenylphosphine and 100 mg of 1,3,5-trimethoxybenzene as internal standard are dissolved once in 4 ml of dimethylacetamide (Example 13) and once in 4 ml of dioxane (Example 14). Both tubes are then placed in the same oil bath at 130° C. (the mixture containing dioxane in a pressure tube) and stirred for 3 hours. A sample is taken in each case before the reaction and after the end of the reaction and the conversion is calculated from HPLC analysis of the samples. In dimethylacetamide (Example 13), 33% conversion (TON=298, TOF=99 h −1 ) was achieved after 3 hours, while in dioxane (Example 14), the conversion was only 2.4%.
Examples 15 and 16
In each case in a Schlenk vessel, 237.6 mg (3.34 mmol) of acrylamide, 0.50 ml (3.71 mmol) of 4-chlorobenzotrifluoride, 0.87 ml (4.08 mmol) of dicyclohexylmethylamine, 0.8 mg (3.7 μmol) of palladium acetate, 3.0 mg (14.9 μmol) of tri(tert-butyl)phosphine and 100 mg of 1,3,5-trimethoxybenzene as internal standard are dissolved once in 4 ml of dimethylacetamide (Example 15) and once in 4 ml of dioxane (Example 16). Both tubes are then placed in the same oil bath at 130° C. (the mixture containing dioxane in a pressure tube) and stirred for 3 hours. A sample is taken in each case before the reaction and after the end of the reaction and the conversion is calculated from HPLC analysis of the samples. In dimethylacetamide (Example 15), 52% conversion (TON=469, TOF=156 h −1 ) was achieved after 3 hours, while in dioxane (Example 16), there was no conversion.
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims. | The present invention relates to a process for the arylation of olefins by reaction of haloaromatics or arylsulfonates with olefins in the presence of a palladium catalyst, a bulky nitrogen base and a dipolar aprotic solvent. | 2 |
This is a continuation of U.S. Ser. No. 09/908,439, filed Jul. 17, 2001; which is a continuation of U.S. Ser. No. 08/672,775, filed Jun. 28, 1996 U.S. Pat. No. 6,287,202; both of which are incorporated herein by reference in their entirety.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates generally to apparatus for playing games of chance, and more particularly to a method and apparatus for allowing a number of players to participate simultaneously in a tournament using a plurality of gaming terminals networked together and under control of a master terminal.
2. Brief Description of the Prior Art
Slot tournaments are a popular slot merchandising practice in casinos. A slot tournament is a group function wherein a player pays a set amount of money to join the tournament, and his entry fee goes into a pot which is paid out to the tournament winner or winners, less the house percentage. The machines used for the tournament are specially configured machines that, upon the issuance of a “start” command by a game controller, allow the players to play as fast as they can without requiring that coins be put into the machines. The wins, or “points”, are accumulated, held and displayed by each machine as points. At the end of a fixed period of time, a “stop” command is given, and all of the machines are disabled. The winner is the person having the highest accumulated score of win points obtained during the tournament period. In most tournaments the winner takes the entire pot.
Currently, tournaments must be run on specially set-up machines in a special area, and there must be at least one live host to run the game. Moreover, the games must be configured, tested and certified as being equal in every respect so that each player has an equal chance to win. Heretofore the machines used for such tournament were carefully selected, but ordinary casino-type slot machines which were enabled at a tournament “start” time and disabled at a tournament “end” time. The accumulated score of each gaming unit had to be visually acquired and recorded by the tournament host, an accounting of all scores accumulated and processed, and a winner orally announced or otherwise posted. The circumstance and machine requirements practically dictated that all machines be located in a single vicinity or room, and that they be dedicated to tournament play. This, of course, limits the opportunity of the general public to have access to the tournament, and makes the tournament costly to conduct on the part of the gaming establishment because it must provide hosts or monitors, dedicate certain machines to tournament use, and provide a suitable facility for the conduct of the tournament.
There is thus a need for a new system and apparatus using state-of-the-art technology to improve all aspects of the conduct of tournament play, e.g., make tournament play more available to all who would enjoy the play, simplify the establishment's monitoring requirements, and reduce overhead expense.
SUMMARY OF THE PRESENT INVENTION
It is therefore a principal object of the present invention to provide a method and system of the type described which makes it possible to conduct a slot tournament using any of a plurality of gaming terminals spread throughout a casino.
Another object of the present invention is to provide a plurality of networked gaming terminals all in communication with, and under control of, a host terminal.
A further objective of the present invention is to provide a method and system of the type described which allows a host or master terminal to automatically communicate with a plurality of gaming terminals and offer to the current player of each terminal the opportunity to play in a tournament without leaving his position on the casino floor.
Still another objective of the present invention is to provide a method and system of the type disclosed which has improved in terminal marketing capability.
Briefly, a preferred embodiment of the present invention includes the provision of a plurality of gaming terminals selectively interlinkable together with a host terminal so that current players of the terminals desiring to participate in group tournament play can be notified of the opportunity and provided with the choice to play or not. If a current player chooses to play, he so signifies, enters his entry fee into the terminal, and awaits start of the event. Upon start of the tournament by the host terminal, the player will play the tournament game over and over as fast as possible to accumulate as many points as possible during a particular pre-announced tournament period. The host terminal will continuously monitor the terminals of all play participants, dynamically record play status, and control termination of the game period. It will also conduct an accounting of the results, issue win results notification, and perhaps provide remote pay-out of game winnings.
An important advantage of the present invention is that it does not require dedicated terminals; i.e., any qualified terminal in the facility can be used and any current player of the gaming units can elect to play.
Another advantage of the present invention is that at most it requires a single terminal operator, and alternatively, the tournament could be run by a pre-programmed but unmanned host terminal.
Still another advantage of the present invention is that it enhances public access to tournament play.
Yet another advantage of the present invention is that play is not limited to a single room, particular machines, or even the same casino facility or location.
These and other objects and advantages of the present invention will no doubt become apparent to those skilled in the art following a review of the detailed description of the preferred embodiment which makes reference to the several figures of the drawing.
IN THE DRAWING
FIG. 1 is a diagram illustrating a plurality of gaming terminals linked together in a network in accordance with the present invention;
FIGS. 2 a and 2 b are generalized logic diagrams illustrating the tournament play process in terms of the master an slave units in accordance with the present invention; and
FIGS. 3 a and 3 b are logic flow diagrams more specifically illustrating the tournament play process implemented by the master and slave units respectively.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring now to FIG. 1 of the drawing, two banks 10 and 12 of gaming terminals (slave units) 14 are illustrated linked in a communications network with a master or host terminal 16 , the latter of which may be configured as a regular gaming terminal or as a stand-alone, dedicated control unit. The network connection can be accomplished by use of any suitable communications media including cable, fiberoptics, wireless or any other suitable data-carrying linkage, and need not necessarily be limited to a local area network (LAN). In fact, the network can be comprised of a wide area network (WAN) or other type of any secure transmission medium communicatively connecting terminals at any location, proximate or remote. Although the gaming terminals are preferably of the state-of-the-art variety manufactured by Silicon Gaming, Inc. of Palo Alto, Calif., it is to be understood that the terminals can take many forms so long as they have the attributes of “sameness”, meaning that when played, each will have the same probability of winning, and each can receive and transmit the data required to control the play and report the results. Having the same probability of winning is referred to in the gaming industry as having the same “percentaging model”.
In accordance with the present invention, it is required that each participating gaming terminal be constrained to have precisely the same tournament period or playing time. In the preferred terminals, means is provided for informing the player that at some subsequent time a tournament is to be conducted, and that, if he wishes to participate, he should so indicate by taking some responsive action, including perhaps the deposit of a specified entry fee. The terminals should have the capability of being placed in a “wait” state during at least the final moments of the game start countdown, and should have the capability of being remotely initialized and controlled for tournament play.
In the preferred embodiment, each terminal has the capability of reporting to the master terminal its current play status, i.e., the number of points accumulated by the player. Each terminal also has the capability of being remotely enabled at the start of the tournament period, and of being remotely disabled at the end of the tournament period, or perhaps at some other arbitrary time before the end of the tournament period if some predetermined winning score has been reached by one of the terminals to end tournament play. In accordance with the present invention, the terminals and network are such that they will allow an operator or programmed host computer or terminal to remotely set up the tournament without requiring actual physical contact with the participating terminals. Only those terminals with players desiring to participate in the tournament will be communicatively linked to the master, and other non-electing terminals will continue to be available for normal game play. Furthermore, when no tournament is being conducted, all of the terminals can revert to regular play status. In accordance with the present invention, using the above-mentioned preferred gaming terminals, players can also set up their own tournaments on an ad hoc basis, and they can be managed by one of the playing terminals or by a non-playing host that is computer-generated.
To implement the preferred embodiment, there must be a network that permits communication with the machines and a master machine or network server that sets up and controls play of the tournament. The master can be programmed with predetermined “regular” starting times and buy-in amounts, and is capable of broadcasting a signal to all machines on the network causing them to run a pre-programmed announcement that a tournament is going to begin in “T” minutes, that the buy-in amount is “X” dollars, and briefly explaining how a slot tournament works. As the time approaches for beginning a tournament, additional notices can be caused to appear on the screen of machines that are currently being played to inform the players of the number of players currently enrolled in the tournament and the size of the jackpot. When the tournament begins, a modified conventional slot game is presented. For example, when the tournament starts, the user will push the “spin” button as fast as he can, without putting additional money in. Each push of the button will cause a new play cycle to be commenced. The winner is the player who accumulates the largest win points in a fixed period of time, usually ten minutes. Upon the assertion of remote commands, all of the games for logged-in terminals will start and end simultaneously.
An exemplary cycle of events for a tournament in accordance with the present invention is as follows:
1) An announcement will be given that a tournament is to begin at a particular time, e.g., “Ten minutes until a new tournament begins.” Only players of eligible machines are notified of the tournament, i.e., those terminals which are capable of playing the same type of game (for example, poker, or a three-reel slot game, etc.), have the same hold percentages, and have tournament software resident on the machines (or are receptive of communicated tournament software).
2) After the announcement is given, each terminal will display an announcement of how players can “buy in”. For example, players who wish to play will insert the amount of money (the “entry fee”) that is required to enter the tournament.
3) Once enough players have signed up (“logged in”) for the tournament, or the time to start the tournament has been reached, the logged-in terminals will be initialized for play start, and actually started simultaneously with other participating machines.
4) During tournament play, the players will accumulate points by playing the game as fast as they possibly can or as fast as they choose to play. Following each play, the game is automatically reset to await the next player input; i.e., there is no need to input a coin or hit a reset button.
5) When the announced tournament period has elapsed, or when a player reaches a predetermined tournament point goal, the tournament will end.
6) The winner will then be determined, notified and paid, and all participating machines will be returned to their normal state. In the usual case, the winner is paid a portion of the tournament pot with payment being made either from the machine itself or manually from a casino host or attendant.
There are basically two ways of starting and conducting a tournament. One uses a master machine that will start and control the progress of the tournament. The other uses a masterless group of machines that are preprogrammed to cooperatively start and jointly manage the tournament. Examples of ways in which a tournament can be started include the following:
1) Manually, via a casino host person using any networked machine;
2) At certain times during the day, for example every three hours, or at some regularly appointed time, a tournament may be started;
3) When a certain number of machines have been committed to participation, for example, when 50 machines have committed players indicating that they wish to participate in the tournament;
4) A group of players may set up a tournament themselves; for example, a group of twelve people might decide that they wish to play a tournament, in which case the machines will allow them to create, start and run their own tournament.
Regardless of the method used to start the tournaments, all machines must begin the game at the same time. Accordingly, a “start” command will be broadcast to all machines to signal the start of the tournament.
When the tournament is underway, players try to earn as many points as possible. Points are quantitatively equal to the normal credits that the slot machine normally pays for winning combinations, except that the points do not represent money in any way. If the player hits a “1,000” point combination during tournament play, he will not win $1,000; he will get 1,000 points or “points”. For a “reel slot machine” style game, players start and play as many spins as possible in order to maximize the number of points earned. A master machine or network controller will continually collect the scores from all machines and form a ranked list to be broadcast to the players.
The players' scores will be communicated to a master terminal where they are accumulated and perhaps transmitted back to the terminals for display. During play, a player may be notified as to his/her standing against other players. The game is complete upon passage of a particular period of time, or upon the determination that one of the players has reached a predetermined winning level of play. Following completion of the game, the winner or winners will be notified, and payment will be made either at the winning terminal or by a host official.
Turning now to FIGS. 2 a and 2 b , the principal operative steps taken by the master and slave units in conducting a tournament are presented in high-level flow diagrams. Referring first to FIG. 2 a , when the master determines ( 20 ) that it is time to start a tournament, it in effect goes out and identifies slave machines ( 22 ) that it thinks are eligible for tournament play, i.e., it identifies terminals that have the appropriate percentaging, have a person sitting there waiting to play, have the right game initialized, etc. This is to say that the master identifies a group of machines that are all potentially available for tournament play. The master then announces ( 24 ) the tournament by broadcasting messages to the players telling them that the tournament is about to begin. It then collects ( 26 ) all the buy-ins (someone inserts money indicating the desire to participate in the tournament), figures out which of these machines are really going to be in the tournament based on the buy-ins, and begins the tournament ( 28 ). During the tournament, it updates ( 30 ) the tournament standings (for its own internal auditing). The standings ( 34 ) could also be broadcast to the playing terminals. Subsequently, the master ends the tournament ( 32 ), and distributes awards ( 34 ) to the winners.
On the slave side, FIG. 2 b , if a particular terminal is in an idle state ( 36 ),i.e., just sitting there unattended, then chances are it is not eligible for tournament play. In order for a terminal to be eligible, it must have a player either playing or waiting to play. A terminal is classified as idle if no player is actively playing a game and for the last three minutes no one has used this machine. A player is identified ( 38 ) if during the last three minutes someone has been using this machines; there is a good chance that someone is currently sitting there playing. Such a machine is thus identified as available for tournament play. An announcement of the upcoming tournament is then sent to this unit to entice the player to enter the tournament. Alternatively, if a machine is found to be sitting idle, the master may go ahead and run the advertisement that a tournament is about to start and perhaps attract someone to sit and play. This is optional and really depends on how one identifies slave-machines as eligible for tournament play.
The slave will receive the tournament announcement ( 40 ) when the master sends it, and if the player elects to play, the slave terminal will perform the buy-in function ( 42 ) by collecting money from the player and sending notice thereof to the master. When the master sends the START PLAY signal ( 44 ) to the terminal to allow the player to begin playing, the player will play the game as fast as possible and accumulate points. An END PLAY sequence ( 48 ) will terminate play when the master determines that either (1) someone has hit a certain point total or (2) a certain amount of time has elapsed. Subsequently, each slave unit will receive notice of the awards as announced by the master, and the winner, or winners, ( 50 ) will receive pay-out from their terminal.
Referring now to FIG. 3 a , the function of the master unit is presented in a more detailed flowchart. Initially, the unit is in a wait state ( 52 ) awaiting a START CYCLE signal to be generated in response to any of several conditions, such as, for example, (1) a particular time of day is reached, (2) an operator has caused a manual start, (3) an ad hoc tournament has been requested by a group of players who want to play a tournament, or (4) some minimum number of in-use machines have been identified, etc. A START signal broadcasts ( 54 ) a slave machine search message identifying the criteria a slave machine should use to determine whether or not it is eligible, i.e., it specifies some set of parameters that uniquely identifies whether or not a slave machine is available for the tournament. For example, the message might indicate that the terminal must have the Fort Knox game and have a 96% hold percentage. Furthermore, it might specify that the game is a three-point game, etc. All of the tournament machines have the same parameters in order to qualify.
After the master broadcasts its search for eligible slave units, it will collect the IDs ( 56 ) of those machines that are available and send some sort of promotional message (advertising to entice the player) to each slave machine ( 58 ), and it will then collect buy-ins ( 60 ) from the slave machines. This cycle will continue until the master determines that it is ready to start the game ( 62 ), i.e., it will constantly search for new machines until some condition is met, e.g. a minimum number of available terminals, a published start time is reached, etc. Once the master is ready to start, it broadcasts ( 64 ) a START signal to all of the committed slave machines, and the tournament is commenced. During the tournament the master may collect point totals ( 66 ) from the slaves as the game progresses and broadcast the score list to the slaves, so that the list can be displayed to the players. The master will continue doing this until the end of the tournament ( 70 ) has been reached, at which time the master sends out an END PLAY message ( 72 ). Several conditions ending the tournament are set out above. Once the tournament has been completed, the master collects all of the final scores ( 74 ), figures out the winner(s) ( 76 ), and sends out pay messages ( 78 ) to the slave machine(s) of the winner(s).
In FIG. 3 b , the slave operational process is depicted. First, the unit determines whether or not it is in use ( 80 ), and if it is in use, it evaluates the tournament parameters and determines if this machine is available for tournament play ( 82 ), has an operator, etc. If the machine is available for tournament play, it waits ( 84 ) for the slave search message from the master. When it receives such a message, it checks the parameters (parms): essentially, it determines whether or not this machine has a tournament game with the right percentaging model and all the parameters needed to match ( 86 ). If not, it merely waits for someone else to come along and ask for a tournament. If it does match, then it plays the invitation movie or some other announcement to attract the player and entice him to buy in. And if the player buys in ( 90 ), the buy-in information is sent ( 92 ) back to the master, and the slave unit waits for a START PLAY signal from the master ( 94 ). In the meantime, the player can continue playing other games on the machine. Once a START PLAY command is received, the player is allowed ( 96 ) to start playing the tournament game, and, as requested, the unit periodically sends the score to the master ( 98 ). The unit may also collect the ranked scores ( 100 ) from the master and display the scores to the player ( 102 ). This may continue until the end of the game, at which time the master will announce the end of the game ( 104 ) by asserting an END GAME signal. At the end of the game, the unit will wait for win information from the master ( 106 ) and, if there are winnings, the unit will pay them to the player ( 108 ).
Although the usual case mentioned above requires as a start condition that a minimum number of terminals be available for play, an alternative play mode might be that if, after a predetermined time has elapsed following the initial tournament announcement (or perhaps an announced start time has passed), the number of available terminals has not reached the minimum, the system may designate a number of terminals (either real or virtual) to run in an automatic play mode and thereby meet the minimum terminal requirement. These automatic terminals would play on behalf of the house, and should one of such terminals win the tournament, the winnings would be retained by the house.
Although the present invention has been described above in terms of a specific embodiment, it is anticipated that alterations and modifications thereof will no doubt become apparent to those skilled in the art. It is therefore intended that the following claims be interpreted as covering all such alterations and modifications as fall within the true spirit and scope of the invention. | Dynamic tournament gaming method and system, including the provision of a plurality of gaming terminals selectively interlinkable together with a host terminal so that current players of the terminals desiring to participate in group tournament play can be notified of the opportunity and provided with the choice to play or not. If a current player chooses to play, he so signifies, enters his entry fee into the terminal, and awaits start of the event. Upon start of the tournament by the host terminal, the player will play the tournament game over and over as fast as possible to accumulate as many points as possible during a particular pre-announced tournament period. The host terminal will continuously monitor the terminals of all play participants, dynamically record play status, and control termination of the game period. It will also conduct an accounting of the results, issue win results notification, and perhaps provide remote pay-out of game winnings. | 6 |
RELATED APPLICATION
This application is related to U.S. Application Ser. No. 61/353,296 filed on Jun. 10, 2010 entitled “BIO-BASED SOLVENT FOR TREATING WEATHERED POLYMERIC MATERIALS”.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a formulation, composition and related methods for protecting and rejuvenating outdoor household PVC materials such as decking and siding and for cleaning and restoring other weathered polymeric surfaces. More specifically, it relates to the use of plant-based solvents and UV protectants to restore the color and appearance of PVC surfaces.
2. Description of the Related Art
A variety of outdoor household products such as siding, doors, fences and decks utilize vinyl resins such as polyvinyl chloride (PVC). Ultraviolet light however causes these materials to discolor and appear weathered due to this environmental exposure. These products are also susceptible to the buildup of mold, mildew, algae and staining. There exists a need for an environmentally friendly, plant-based solvent and UV protectant composition for cleaning and rejuvenating outdoor household PVC materials that is safe, effective, economical and requires a minimum amount of labor.
SUMMARY OF THE INVENTION
In one embodiment, the present invention provides for a formulation comprising: ethyl lactate; at least one hydrocarbon solvent; and at least one benzotriazole UV protectant wherein the formulation is applied to a polymeric material for restoration of color and appearance.
In another embodiment, the formulation further comprises D-limonene. In a further embodiment, the D-limonene is from about 1% to about 10% of said formulation. In another further embodiment, the D-limonene functions as a cleaning and odor removing agent.
In yet another embodiment, ethyl lactate is from about 20% to about 95% of said formulation. In still another embodiment, the hydrocarbon solvent is from about 1% to about 10% of said formulation. In still yet another embodiment, the UV blocker is from about 1% to about 15% of said formulation.
In a further embodiment, the formulation may be applied a fiberglass gelcoats. In yet a further embodiment, ethyl lactate and the hydrocarbon solvent softens a surface of the polymeric material and the UV protectant chemically or mechanically bonds to the polymeric material to restore color and appearance.
In still a further embodiment, the present invention relates to a polymeric material color restoration composition comprising: at least one plant based solvent; and at least one UV protectant. In still yet a further embodiment, the plant based solvent comprises ethyl lactate from about 20% to about 95% of the composition. For purposes of this invention, the term “plant based solvent” shall be defined as any solvent that is derived or can be derived from plants including synthetically manufactured solvents.
In another embodiment, the UV protectant is from about 1% to about 15% of the composition. For purposes of this invention, the term “UV Protectant” shall be defined as any additive incorporated into the mixture that will provide protection from UV degradation of the surface, including, but not limited to, benzotriazoles, metal oxides and other related chemical and mixtures thereof, and may perform as free radical scavengers, filters blockers or other various methods of UV protection.
In still another embodiment, the composition further comprises at least one hydrocarbon solvent from about 1% to about 10% of the composition. For purposes of this invention, the term “hydrocarbon solvent” shall be defined as any chemical or mixture of chemicals whose molecules are primarily carbon and hydrogen that may function as a solvent and/or that has properties that can soften or dissolve materials within that material's solubility parameter.
In still yet another embodiment, the composition further comprises at least one cleaning and odor removing agent. In a further embodiment, the cleaning and odor removing agent is from about 1% to about 10% of the composition. For purposes of this invention, the term “cleaning and odor removing agent” shall be defined as any chemical or substance that clean or remove odor.
In another further embodiment, the plant based solvent is selected from a group consisting essentially of plant based esters and hydrocarbons, esters, hydrocarbons and mixtures thereof. In yet another further embodiment, the hydrocarbon solvent is selected from a group consisting essentially of long chain hydrocarbons. In still another further embodiment, the UV protectant is selected from a group consisting essentially of benzotriazoles, metal oxides and mixtures thereof.
In still yet another further embodiment, the cleaning and odor removing agent is selected from a group consisting essentially of terpines, plant based terpines and mixtures thereof.
In another embodiment, the present invention provides for a method of manufacturing polymeric material color restoration composition comprising admixing at least one plant based solvent and at least one UV protectant.
In order to fulfill the need for a more eco-friendly cleaning and restorative solution for outdoor structures which contain PVC, the present invention has been created. The invention utilizes plant-based solvents to modify the PVC surface giving the appearance of color restoration. In addition, the invention utilizes UV absorbers and HALS (hindered amine light stabilizers) to extend the color retention of the surface. The UV absorbers prevent the degradation of both coatings and substrates by filtering out harmful UV energy of sunlight. The HALS stabilizers act as radical scavengers and inhibit the photo-oxidative breakdown reactions. Both of these effective ingredients work together synergistically to provide enhanced protection and prolonged coating durability. In addition to the invention's utility as a restorative and rejuvenating composition, it also displays cleaning properties and can be used to remove scuff marks, rust, oil stains and other stains on the above-mentioned polymeric surfaces.
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.
DETAILED DESCRIPTION OF THE INVENTION
As required, detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention that may be embodied in various forms. The figures are not necessarily to scale, some features may be exaggerated to show details of particular components. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention.
In one embodiment of the invention, a liquid composition utilizes ethyl lactate as its primary active ingredient. It may also use up to 9-10% of a traditional hydrocarbon solvent. Ethyl lactate is the primary active ingredient for the cleaning properties of the invention which also utilizes d-limonene as a lesser active ingredient to aid its cleaning properties. In one embodiment, the formulation of the invention comprises a concentration of 94-5% by volume of a material sold under the name of Bio-Solv™ sold by MAS Epoxies located at 2615 River Road, Cinnaminson, N.J. This product contains 91% ethyl lactate and a solvent containing ethyl-3 at 8% and BHT at 1% concentration. In addition to the Bio-Solv™ ingredient, d-limonene in the amount of 6% is included. An enhanced version of the invention utilizes an organic UV inhibitor in the range of .25% to 5%. An example is Tinuvine 5151 produced by CIBA Specialty Chemicals at a concentration of 1.66%, with the other ingredients reduced proportionately. Other ingredients that have been tested include soy methyl ester as well as other plant-based solvents. The inclusion of a UV inhibitor/blocker with a PVC restorative solvent is thought to be a unique aspect of the invention. The UV inhibitors combine with the dissolved PVC surface to retain the inhibitor within the dissolved host material. This chemical action has been found to greatly extend the UV inhibiting life of the treatment compared to prior art products.
The composition of the invention is used to clean and restore color to weathered or aged surfaces, primarily PVC cap stock, acrylic cap stock, ASA cap stock, fiberglass and other polymeric surfaces. These surfaces typically include household materials such as decks, siding, deck railing, piping and marine surfaces. The invention has been found effective in restoring the color and removing stains from these plastic surfaces. The liquid composition of the invention is employed very simply by direct topical application using a 100% cotton cloth or mop. It can also be sprayed on with spray apparatus well known in the art. The invention provides a one-step cleaning and conditioning of conditioning of surfaces and materials containing PVC while restoring and beatifying their original color. The present invention works by a chemical re-extrusion of the PVC surface by melting microcrazing cracks together. This process changes the way light is reflected and refracted from the surface, giving the appearance of restoring the original color. The bio-based solvents soften the PVC surface and allow the UV inhibitor/blocker to chemically bond to the PVC therefore extending the life of the “color” of the PVC. In one embodiment, the hydrocarbon solvent is butylated toluene.
The present invention as demonstrated by the composition of one embodiment described above and has been found to extend the life of the PVC surface color, providing a cleaning and restorative result in a one-step simple application. The inventive composition provides advantages over the prior art because it utilizes plant-based, non-hazardous, non-flammable constituents. It is shown to be highly effective in restoring color to faded, aged or weathered surfaces while cleaning stains. Incorporation of the UV absorbers and HALS can extend the life of the color by greater than 50%. The present compound is also found to be effective in restoring fiberglass gel coats.
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 composition and operation shown and described, and accordingly, all suitable modifications and equivalents may be resorted to, falling within the scope of the invention. | A composition for restoration and treatment of PVC materials is provided and the composition comprises: at least one plant based solvent; and at least one UV protectant, and the plant based solvent comprises from about 20% to about 95% of said composition and the UV protectant is from about 1% to about 15% of said composition. | 2 |
REFERENCE TO PROVISIONAL APPLICATION
[0001] This application is based on and hereby refers to U.S. Provisional Patent Application Ser. No. 60/695,534, filed Jul. 1, 2005, having the same title as appears above, the entire contents of which are incorporated herein by this reference.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to above-ground swimming pools, particularly to spas attached to such pools.
[0004] 2. Background Art
[0005] Exterior spas, or hot tubs, have steadily grown in popularity in recent years. More and more new pool purchasers are choosing to include a spa unit with their swimming pool. While combined swimming pool and spa assemblies are not new, most known prior art describes spas combined with in-ground pools.
[0006] U.S. Pat. No. 4,240,165 issued Dec. 23, 1980 to Kyrias, and U.S. Pat. No. 4,930,168 issued Jan. 5, 1990 to Ferlise, both disclose a removable partition to be installed in a pool to define a space to be used as a spa. However, the usable pool space is considerably reduced when the spa partition is in place.
[0007] Some patents, like U.S. Pat. No. 4,238,859 issued Dec. 16, 1980 to Badon, teach spill-over type spas without direct access between the spa and the swimming pool. This patent provides for a spa which is adjacent to a swimming pool, with a transition section between the two resting on the upper peripheral edge of the swimming pool and permitting water to spill over from the spa into the pool. The spa remains a completely separate body of water otherwise.
[0008] U.S. Pat. No. 5,727,264 issued Mar. 17, 1998 to Craig et al., discloses a pre-fabricated in-ground swimming pool with the ability to readily permit the addition of an add-on spa. The spa is devised to be entered from the outside, not from the swimming pool, as there is no passageway between the swimming pool and the added spa.
[0009] In addition, spas are usually fabricated as a single rigid shell, and as such take a considerable amount of storage space which greatly increases transport costs.
[0010] Therefore, there exists a need for a spa designed to be attached to an above-ground swimming pool which can be easily mass transported, and act both as an independent body of water from the pool and as a continuation of the pool when not in function.
SUMMARY OF INVENTION
[0011] It is therefore an aim of the present invention to provide an improved spa for attachment to an above-ground swimming pool.
[0012] Therefore, in accordance with the present invention, there is provided a spa for an above-ground swimming pool having a first opening in a wall panel thereof, the spa comprising a shell adapted to receive water therein, the shell including a perimeter wall, a second opening in the perimeter wall, a support structure adapted to support the shell adjacent to the swimming pool so that the first opening corresponds with the second opening, thereby defining a passage providing fluid communication between the swimming pool and the spa, and a removable partition for closing the passage such that the spa becomes an independent body of water from the swimming pool.
[0013] Further in accordance with the present invention, there is provided a spa comprising a shell, the shell including an enclosure for receiving water therein, the enclosure defining a floor surface, at least one bench defining a seating surface at an adequate height for receiving a user in a seated position such as to be comfortably immersed when the enclosure is filled with water, a top coping defining a top end of the shell, and an outer wall extending downwardly from the top coping, the outer wall having a bottom end which is lower than the seating surface and higher than the floor surface, such that the shell is stackable onto a similar shell with the bottom end of the outer wall resting on the top coping of the similar shell.
[0014] Also in accordance with the present invention, there is provided an enclosure adapted to receive water therein and having a height of H, the enclosure having an outer wall extending downwardly from a top thereof for a height of HW, HW being smaller than H, and the enclosure being stackable on similar enclosures such that a stack height is defined by H+(n-1)*HW, where n is the number of enclosures in the stack.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] Having thus generally described the nature of the invention, reference will now be made to the accompanying drawings, showing by way of illustration a preferred embodiment thereof and in which:
[0016] FIG. 1 is a perspective view of an above-ground swimming pool and spa assembly according to a preferred embodiment of the present invention;
[0017] FIG. 2 is a top perspective view of the spa of the assembly of FIG. 1 ;
[0018] FIG. 3 is a bottom perspective view of the spa of FIG. 2 ;
[0019] FIG. 4 is a perspective partial view showing a removable door panel of the assembly of FIG. 1 ;
[0020] FIG. 5 is a perspective view showing the installation of a pool top ledge over an opening of the spa of FIG. 2 ;
[0021] FIG. 6 is a perspective view of a support structure supporting the spa of FIG. 2 on the ground;
[0022] FIG. 7 is a perspective view of exterior spiral steps installed on a spa according to the present invention;
[0023] FIG. 8 is a perspective view of a pool an spa assembly including a dome-shaped cover on the spa, according to the present invention; and
[0024] FIG. 9 is a perspective view of a stack of spas similar to the spa of FIG. 2 .
[0025] FIGS. 10 A-B are views of an alternate version of the spa of FIG. 2 .
[0026] FIGS. 11-12 are views of another alternate version of the spa of FIG. 2 .
[0027] FIGS. 13 A-C are views of a ladder assembly useful in connection with the assembly of FIG. 1 and alternate spas.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0028] Referring now to FIG. 1 , an above-ground swimming pool and spa assembly 10 includes a pool 12 and a spa 14 . The pool 12 is preferably circular and can be substantially similar to that disclosed by Dallaire et al. in U.S. Pat. No. 5,054,135 or by Shaanan et al. in U.S. Pat. No. 5,875,500, which are both incorporated herein by reference. In a preferred embodiment, the pool 12 generally comprises a wall panel 11 retained by a plurality of vertical posts 17 extending between an annular base or rail member 15 and an annular top ledge 19 . The pool 12 has a flat floor surface 20 which is generally leveled with the ground.
[0029] Referring to FIGS. 1 to 3 , the circular spa 14 has a smaller diameter than the pool 12 , and is integrated therewith such that the two circular elements meet at a common point. A common rectangular opening 24 in the wall panel 11 of the pool 12 allows access between the pool and the spa. The spa 14 is formed as a one-piece integrally molded resin shell. A double wall 26 defines a spa perimeter and includes an inner wall 28 and an outer wall 30 . The inner wall 28 is molded such as to include a series of steps 44 for entering the spa as well as circumferential benches 42 . Head rests (not shown) can be provided on a top edge of the inner wall 28 for added comfort. The inner wall 28 flows into a floor surface 31 , which preferably includes a lower step 22 . The inner and outer walls 28 , 30 are interrupted by the opening 24 which is preferably located opposite of the steps 44 . The inner and outer walls 28 , 30 are bridged at a top end thereof by a top annular coping 36 , with a space between the walls 28 , 30 defining an annular cavity 34 . The annular cavity 34 provides space for the necessary spa plumbing, such as a water return pipe, a drain, and a hot water inlet (not shown). A plurality of cup holders 41 are provided in or near the top annular coping 36 .
[0030] As shown in FIG. 6 , it is also considered to include other user convenience details in the top annular coping 36 such as storage trays 37 , additional cup holders 41 , and a control panel 39 for water temperature and air inlet regulation. A curved towel rack 54 is also provided at the rear of the spa element 14 on the outer wall 30 .
[0031] Referring to FIG. 4 , a removable partition or access door panel 16 , which is slightly wider than and at least as high as the opening 24 , can block the opening 24 such as to provide isolation of the spa 14 from the pool 12 , thereby allowing heating of the spa water without much heat loss to the cooler pool water. When the access door panel 16 is removed, the unheated spa area becomes part of the swimming pool. In a preferred embodiment, the access door panel 16 slides down into vertical grooves 32 located in the spa wall 26 on each side of the opening 24 . FIG. 5 shows the installation of a pool top ledge 19 over the opening 24 , when the panel 16 is closed. The top ledge 19 thus retains the panel 16 in the closed position.
[0032] As the depth of the spa 14 is less than that of the pool 12 , and the top annular coping 36 of the spa 14 and the top ledge 19 of the pool 12 are level, the spa 14 has to be elevated with respect to the flat floor surface 20 of the pool 12 . Therefore, support is necessary for maintaining the spa 14 leveled at the desired height. Referring to FIG. 6 , this support is provided by a base support structure 66 combined with a wall reinforcing structure 72 . The base support structure 66 comprises a plurality of vertical tubular support members 68 extending from a bottom of the spa 12 and connected at their lower end to shorter horizontal base support members 70 which rest on the ground. The wall reinforcing structure 72 comprises an horizontal T-shaped base member 76 made of square section tubing which rests on the ground. Vertical steel tubes 74 , also having a square section, extend upwardly from end-points of the base member 76 . A thin, roughly semicircular steel wall section 64 extends downwardly from the outer wall 30 and is supported by the vertical tubes 74 . The wall section 64 is easily removable for access to the enclosed spa piping and support structures.
[0033] Referring to FIG. 7 , exterior spiral steps 48 with an integrated spiral handrail 52 can be provided for entrance into the spa from ground level. The exterior spiral steps 48 are molded as a single piece resin shell. A space beneath the steps can serve as a convenient location for the pool pump and filtration system. The exterior spiral steps 48 include a top landing 50 which extends to the top annular coping 36 of the spa wall 26 , and which is preferably aligned with the interior spa steps 44 . It is also considered to provide an additional handrail (not shown) inside the spa 14 such as to facilitate getting in and out thereof safely.
[0034] Referring to FIG. 8 , a retractable dome shaped cover 18 serves to provide protection to the spa occupants from the sun and wind. The cover 18 comprises a plurality of semicircular rib members 56 which rotate about two common hinges 58 . A flexible cover 60 is fixed over the ribs 56 . The flexible cover 60 can be made of any protective material, but is preferably made of a translucent UV-proof material for aesthetic purposes and to preserve visibility. Rib locking means (not shown) are provided such as to permit the spa cover 18 to be fixed in various stages of closure, between fully enclosing the spa and being left fully open. When not in use, the cover 18 can be completely opened by folding it down so that all the rib members 56 are aligned with the top coping 36 of the spa.
[0035] Referring to FIG. 9 , the integrally molded shell of the spa 14 is such as to be stackable for easy mass transport. When two spas 14 are stacked, a bottom end of the outer wall 30 of the top spa will rest against the top coping 34 of the bottom spa. Thus, the outer wall 30 needs to be generally vertical (i.e. not inclined) so that the bottom end of the outer wall 30 can be vertically aligned with the top coping 34 of a second spa. The shape of the spa 14 is designed so as to be able to insert one spa into another without interference at a depth of HW, which is the height of the outer wall 30 . In particular, the benches 42 are set so that their underside is less than HW from the top landing 50 . In other words, the sum of the distance from the top landing 30 to the seating surface of the benches 50 and the thickness of the wall of this seating surface is less than HW. The opening 24 also needs to be sufficiently large toward a top end thereof so that the step 22 of another spa can be lowered into it at a depth of at least HW without interference.
[0036] According to this design, and as illustrated in FIG. 9 , a stack of n spas each having a spa height of H will have a total height of H+(n-1)HW. In other words, each spa which is stacked on another will only increase the total height of the stack by HW. The spa is preferably designed such as to have a value of HW which is at most one half (½) of the value of H. Accordingly, a stack of 3 spas can be as short as 7.5 feet in height, which allows for a significant number of spas to be transported in a limited container space.
[0037] Illustrated in FIGS. 10 A-B is alternate spa 100 for use with pool 12 as part of assembly 10 . Spa 100 may generally be similar to spa 14 ; preferably, however, spa 100 includes a tapered common opening 104 (i.e. having cross-section like that of a truncated cone) with pool 12 into which a removable door panel may be fitted. Removable top ledge portion 108 may be used to retain the door panel in place. Alternatively, top ledge portion 108 may be employed even when the door panel is removed so as to maintain upper definition of the spa 100 . Yet alternatively, spa 100 may comprise a water spillway, so that water may spillover from spa 100 into pool 12 whether or not top ledge portion 108 and the door panel are present.
[0038] FIGS. 10 A-B additionally illustrate hand rails 112 , one or more of which optionally may be incorporated into annular coping 116 of spa 100 . Rails 112 , if present, are configured to facilitate entry into spa 100 by persons climbing ladder 180 (see FIGS. 13 A-C). Rails 112 thus are generally aligned with steps 44 , so as to permit persons entering the spa 100 easily to do so via the steps 44 . As shown in FIGS. 10 A-B, rails 112 need not be identical in appearance, but instead may differ as appropriate or desired.
[0039] Depicted in FIGS. 11-12 are additional optional aspects of assembly 10 with pool 12 and another alternate spa 120 . Illustrated especially in these figures are optional head rests 124 aligned with curved recesses 128 in inner wall 132 , creating a comfortable area for the back and head of an occupant of spa 120 . Head rests 124 may be molded into or otherwise formed as part of top annular coping 136 ; alternatively, they may be attached to coping 136 or inner wall 132 (or both).
[0040] Also optionally connected to copying 136 (or to outer wall 140 ) are one or more support bars 144 to which seats 148 are attached externally of outer wall 140 . Seats 148 , if present, permit persons to sit outside spa 120 yet converse with persons within spa 120 , utilize coping 136 as a platform for food, beverages, or other items, or use cup holders or other features of spa 120 . In the versions illustrated in FIGS. 11-12 , each seat 148 may comprise base 152 and footrest 156 . Those skilled in the art will, however, recognize that other configurations of seats 148 may be employed instead.
[0041] Detailed particularly in FIGS. 13 A-C is optional ladder assembly 160 of the present invention. Ladder assembly 160 may comprise spaced rails 164 , each of which rails 164 is generally U-shaped and connected to the other rail via bar 166 . One leg 168 of each rail 164 preferably is configured to contact the ground (or whatever base is used for ladder assembly 160 ), while the other leg 172 of each rail may, but need not, contact the ground (as shown in FIGS. 13 A-C). Connector 176 may connect each leg 172 to ladder 180 , whereas connector 184 may connect ladder 180 to each of legs 168 and 172 . Ladder 180 , further, may include one or more rungs 188 .
[0042] Also shown in FIGS. 13 A-C is cover 192 . Cover 192 preferably is fitted into slots 196 in rails 164 so that some frictional interference occurs, but so that cover 192 remains able to slide within the slots 196 . FIG. 13A depicts cover 192 in an “open” position, in which rungs 188 are uncovered and available for use. In FIG. 13B , cover 192 is shown as having been moved so that its leading edge 200 covers (only) top rung 188 A. FIG. 13C illustrates cover 192 having been moved so as to cover all rungs 188 , rendering the rungs 188 inaccessible for use. This latter illustration is thus of cover 192 in its “closed” position.
[0043] The embodiments of the invention described above are intended to be exemplary. Those skilled in the art will therefore appreciate that the forgoing description is illustrative only, and that various alternatives and modifications can be devised without departing from the spirit of the present invention. Accordingly, the present invention is intended to embrace all such alternatives, modifications and variances which fall within the scope of the appended claims. | A spa for an above-ground pool, the spa comprising a shell adapted to receive water therein and including a perimeter wall, an opening in the perimeter wall, a support structure adapted to support the shell so that the opening corresponds with a pool opening to define a passage providing fluid communication between the pool and the spa, and a removable partition for closing the passage. Also, a spa comprising a shell including an enclosure for receiving water therein, at least one bench defining a seating surface at an adequate height, a top coping defining a top end of the shell, and an outer wall extending downwardly from the top coping and having a bottom end which is lower than the seating surface, such that the shell is stackable onto a similar shell with the bottom end of the outer wall resting on the top coping of the similar shell. | 0 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a roller type linear guideway, linear guideway is widely used on machinery trade, automatic equipments, measuring machines, electronic instruments, and the likes. However, the roller type linear guideway is used on large machine.
[0003] 2. Description of the Prior Arts
[0004] Linear guideway generally comprises a rail, a slide block mounted on the rail, and a plurality of rolling elements disposed between the slide block and the rail. If the rolling elements are cylindrical rollers, the guideway is called roller type linear guideway.
[0005] A rolling-element-circulating system of the roller type linear guideway generally comprises the rolling-element-retainer, the return path, the return unit, and etc. the circulating system of the roller type linear guideway is generally made up of a plurality of independent components or integrally formed by plastic ejection.
[0006] JP Patent 2002-54633 discloses a rolling-element circulating system which is made up of a plurality of independent components, wherein the rolling-element retainers 11 , 12 , 13 , the return path 14 and the return unit (including 15 a and 15 b ) are independent components. The respective independent components are not integral with the slide block 4 , there are too many independent components, and thus the assembly is complicated and time-consuming.
[0007] JP Patent 7-317762 discloses a rolling-element circulating system that is made by integral plastic ejection, in which, the slide block 13 is used as a part of the plastic ejection mold, and then the rolling-element supporting structure (the structure 17 which is made up of 30 , 31 and 32 ), the return path 10 and the return unit ( 16 and 19 ) are integrally formed by plastic ejection. If the slide block is big size, then the size of the corresponding mold should be large. Furthermore, the plastic ejection process needs to be controlled precisely, and the difficulties are relatively increased. In this case, the dimension tolerance of the slide block must be controlled precisely before plastic ejection, so that the slide bock can be fully fitted into the mold. In addition, the supporting structure is difficult to be produced since it has long and thin sidewalls.
[0008] The present invention has arisen to mitigate and/or obviate the afore-described disadvantages.
SUMMARY OF THE INVENTION
[0009] The primary object of the present invention is to provide a roller type linear guideway which can take the place of the ball type linear guideway. The contact surface (line-contact) of the roller is much larger than that of the rolling ball, the load capacity of the roller is accordingly larger than that of the rolling ball. Therefore, the roller type linear guideway is normally used on the large scale machine.
[0010] The roller type linear guideway in accordance with the present invention generally comprises: an elongated rail having four sliding surfaces, on the rail is mounted a slide block which is provided with four reflow passages and four sliding surfaces. Two half recirculating-models are inserted from both ends of the slide block with a specific angle so as to form a complete recirculating model. A roller mold is made up a plurality of roller and circulates in the recirculating model, and then two ender caps are assembled to both ends of the slide block.
[0011] In addition, the circulating mold is made up of a plurality of U-shaped half recirculating pieces, the half recirculating piece is integrally formed with a plurality of return blocks, supporting ribs and return half-tubes, each two half recirculating pieces are combined into a half recirculating-model, the half recirculating-model comprises a return portion, a supporting portion and a reflow portion, the return portion is connected between the supporting portion and the reflow portion, the return portion is provided with an outer return path and an inner return path, the recirculating-model is provided with two recirculating paths for the roller-model, the two recirculating paths intersect at the return portion to form a X-type turn, so that the roller-model will circulate in the recirculating paths and will change its direction through the X-type turn in the return portion. The inner return path of a half recirculating-model is connected with the supporting portion and the return portion of this half recirculating-model, and then is connected to the outer recirculating path of another half recirculating-model, so as to form a complete recirculating path.
[0012] In addition, the roller-model in accordance with the present invention can be made up of a plurality of rollers, or can be made up of a plurality of rollers and partitions, the partition can be a chain-like structure or can be a single structure.
[0013] The recirculating-model in accordance with the present invention is made up of a plurality of half recirculating pieces, therefore, it doesn't need a lot of accessories, so that the time of fabrication can be reduced and the manufacturing cost is saved.
[0014] The present invention will become more obvious from the following description when taken in connection with the accompanying drawings, which show, for purpose of illustrations only, the preferred embodiments in accordance with the present invention.
BRIEF DESCRIPTION OF THE DRAWINGS
[0015] FIG. 1 is an exploded view of a roller type guideway in accordance with the present invention;
[0016] FIG. 2 shows an end surface of a roller type guideway in accordance with the present invention;
[0017] FIG. 3 is an exploded view for showing the half recirculating-model of the roller type linear guideway in accordance with the present invention;
[0018] FIG. 4 is another exploded view for showing the half recirculating-model of the roller type linear guideway in accordance with the present invention;
[0019] FIG. 5 is a partial amplified view of FIG. 4 ;
[0020] FIG. 6 is a perspective assembly view of a complete recirculating-model of FIG. 4 ;
[0021] FIG. 7 is a cross sectional view taken along the line of A-A of FIG. 7 ;
[0022] FIG. 8 is a cross sectional view taken along the line of B-B of FIG. 6 ;
[0023] FIG. 9 is a cross sectional view taken along the line of C-C of FIG. 6 ;
[0024] FIG. 10 is a cross sectional view of the end cap of FIG. 1 ;
[0025] FIG. 11 is a roller-model in accordance with another embodiment of the present invention;
[0026] FIG. 12 is a partition of the roller-model of FIG. 11 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0027] FIG. 1 is an exploded view of a roller type guideway in accordance with the present invention. FIG. 2 shows an end surface of a roller type guideway in accordance with the present invention, wherein the roller type guideway is not equipped with end cap. The roller type guideway comprises: a rail 10 which is an elongated structure having four sliding surfaces 11 and 12 , a slide block 20 having four reflow passages 21 , 22 and four sliding surfaces 23 , 24 , a pair of half recirculating-models 30 , two ender caps 40 , a roller-model 50 which is made up of a plurality of rollers, a dust-proof plate 60 and two end seals 70 . The slide block 20 is mounted on the rail 10 and slides thereon, the sliding surfaces 11 , 12 abut against the sliding surfaces 23 , 24 of the slide block, and the roller-model 50 is disposed in the space defined by slide surfaces 11 , 12 of the rail 10 and the slide surfaces 23 , 24 of the slide block 20 . The half recirculating-models 30 are inserted in the reflow passages 21 , 22 of the slide block 20 . The end caps 40 are assembled at both ends of the slide block 20 , the dust-proof pieces 60 are installed in the clearances at the lower part of the slide block for preventing dust. The end seals 70 are disposed at the outer side of the ender caps 40 for stopping the dirty oil or dust on the rail 10 from entering into the slide block 20 .
[0028] FIG. 3 is an exploded view for showing the half recirculating-model of the roller type linear guideway in accordance with the present invention. FIG. 4 is another exploded view for showing the half recirculating model of the roller type linear guideway in accordance with the present invention. FIG. 5 is a partial amplified view of FIG. 4 . Each of the half recirculating-models 30 is made up of a pair of U-shaped half recirculating pieces 30 a , 30 b which are integrally formed with return blocks 33 a , 33 b , supporting ribs 31 a , 31 b and return half-tubes 32 a , 32 b . The return block 33 a of the U-shaped half recirculating piece 30 a is connected between the supporting rib 31 a and the reflow half-tube 32 a , and the return block 33 b of the U-shaped half recirculating piece 30 b is connected between the supporting rib 31 b and the reflow half-tube 32 b . The return blocks 33 a and 33 b are provided with inner return surfaces 333 b and outer return surfaces 332 a . The half recirculating model is provided with a groove 322 along the recirculating path of the roller type linear guideway for guiding the motion of the roller-model (not shown). The width of the groove 322 is larger than one third the diameter of the roller, and the half recirculating-model is further provided with an oiling groove 34 b and oil scuppers 341 b , 342 b . An end of the supporting ribs 31 a , 31 b that is not connected to the return blocks 33 a , 33 b is provided with a fixing pin 311 a , 311 b , respectively. After the two half recirculating pieces 30 a and 30 b are combined together through the positing pins 321 b , 331 b and the locating holes (not shown), the supporting ribs 31 a , 31 b will be combined into a supporting portion 31 , the reflow half-tubes 32 a and 32 b will be combined into a reflow portion 32 , and the return blocks 33 a and 33 b will be combined into a return portion 33 . On the outer surface of the reflow portion 32 are provided a plurality of projections 35 a which are to be inserted in the reflow passages 21 , 22 of the slide block 20 and serve as a positioning means. A recirculating space 323 is defined in the reflow portion 32 for circulation of the roller-model (not shown). The return portion 33 is provided with an inner return path (not shown) that is made up of inner return surfaces 333 b , an outer return path 332 that is made up of outer return surfaces 333 a , an oiling entrance 34 made up of the oiling grooves, an outer drainage port 341 made up of the oil currages 341 b , and an inner drainage port (not shown) made up of oil scuppers 342 b . The lubricant oil, after entering the oiling entrance 34 , will flow via the outer drainage port 341 to the inner and the outer return path so as to lubricate the roller-model. In addition, the two half recirculating-models 30 are inserted from both ends of the slide block 20 with a specific angle of 90 degrees so as to form a complete recirculating-model.
[0029] FIG. 6 is a perspective assembly view of a complete recirculating-model of FIG. 4 . FIG. 7 is a cross sectional view taken along the line of A-A of FIG. 7 . FIG. 8 is a cross sectional view taken along the line of B-B of FIG. 6 . FIG. 9 is a cross sectional view taken along the line of C-C of FIG. 6 . The roller mold 50 comprises a plurality of rollers and chain-like partition, the recirculating-model is provided with two recirculating paths for the reception of the roller-model 50 , wherein one of the recirculating paths is accommodated with a roller-model 50 and the other of the recirculating paths is not accommodated with the roller-model 50 . The reflow space 325 is made up of the two half reflow tubes 32 a and 32 b , the slide space 312 is made up of the two supporting ribs 31 a and 31 b , and the groove 322 serves for guiding the partitions among the roller-model 50 (not shown). As shown in FIG. 7 , which is a cross sectional view of showing the right side of the return portion of the recirculating-model, the recirculating path accommodated with the roller-model 50 extends from the inner return path (not shown) of the right side of the recirculating-model, and changes from load condition (or circulating condition) to circulating condition (or load condition). However, the recirculating path without the roller-model 50 is the outer return path 332 of another half recirculating-model which is located at the right side of the recirculating-model. The two lines of recirculating paths intersect at the return portion 33 to form a X-type turn, so that the roller-model 50 is able to circulate in the recirculating path and to change its direction through the X-type turn of the return portion. With reference to FIG. 9 , which is a cross sectional view of showing the left side of the return portion of the recirculating-model, the recirculating path accommodated with the roller-model 50 extends from the inner return path (not shown) of the left side of the recirculating-model, and changes from load condition (or circulating condition) to circulating condition (or load condition). However, the recirculating path without the roller-model 50 is the outer return path 332 of another half recirculating-model which is located at the left side of the recirculating-model. The two lines of recirculating paths intersect at the return portion 33 to form a X-type turn, so that the roller-model 50 is able to circulate in the recirculating path and to change its direction through the X-type turn of the return portion.
[0030] FIG. 10 is a cross sectional view of the ender cap of FIG. 1 . The ender caps 40 are assembled to both ends of the slide block 20 of FIG. 1 , each of the ender caps 40 is provided with a return curve-surface 47 which is used to cooperate with the outer return path 332 of the half recirculating-model 30 in FIG. 5 , so as to prevent the roller-model 50 from being fallen off the recirculating path when passing through the outer return path 332 . The ender caps 40 are further provided with a plurality of fixing holes 43 , 44 which are employed to position the supporting ribs 31 a , 31 b by cooperating with the fixing pins 311 a , 311 b . A plurality of grooves 46 are formed on the ender caps 40 for cooperating with the reflow portion 32 of the half recirculating-model 30 . To improve the lubricating effect, an oiling aperture 41 is formed on each of the ender caps 40 and connected to both sides of the ender caps 40 via oilways 42 . At the end of the oilways 42 are provided oil spaces 45 for cooperating the oiling entrance 34 on the return portion 33 of the half recirculating-model 30 , so that the lubrication can be poured into oiling aperture 41 and flows to the oil spaces 45 via the oilways 42 , and then flows to the oiling entrance 34 of the half recirculating-model 30 for lubricating the roller-model (not shown).
[0031] FIG. 11 is a roller-model in accordance with another embodiment of the present invention. FIG. 12 is a partition of the roller-model of FIG. 11 . The roller-model 50 comprises a plurality of rollers 51 and the partitions 52 , 53 . The partition 52 is a chain-like structure which is made up of a plurality of spacing portions 521 and a chain 522 , the rollers 51 are separated from one another by the spacing portions 521 and linked together by the chain 522 . A plurality of troughs 523 are formed on the chain structure for enabling the roller mold to change moving direction during circulation. Another type partition 53 is a one-piece structure comprised of a spacing portion 531 and a pin portion 532 and serves to separate the rollers 51 .
[0032] While we have shown and described various embodiments in accordance with the present invention, it should be clear to those skilled in the art that further embodiments may be made without departing from the scope of the present invention. | The present invention relates to a roller type linear guideway which comprises the rail, the slide block, the roller-model, the recirculating-model, and the ender cap. The recirculating-model is make up of two half recirculating-models which are assembled together at a specific angle, and each of the half recirculating-models comprises two U-shaped recirculating piece which includes a return portion, a supporting portion and a reflow portion, the recirculating paths of the roller-models intersect to form a x-type turn. Therefore, there are no a lot of accessories, that can reduce time of fabrication and can save the cost of manufacture. | 5 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application claims the benefit of U.S. Provisional Application No. 62/212,828 filed on Sep. 1, 2015, incorporated by reference herein in its entirety.
BACKGROUND
Advances in processors, battery life, and visual displays have vastly improved the performance possibilities of laptop computers. With wireless mobility and connectivity becoming a necessity in today's business environment, many businesses and entrepreneurs have chosen to use laptop computers in lieu of desktops in the workplace. However, laptops typically have smaller keyboards than the standard keyboards utilized with desktops, and a standard mouse is generally preferred by users in the office environment over the built-in touchpad or tricks of laptop computers. In addition, prolonged use of a laptop alone can be an uncomfortable experience for the user.
A docking station allows laptop computers to become a substitute for a desktop computer without sacrificing the mobile computing functionality of the machine. For example, port replicator-type docking stations allow multiple peripherals—such as a keyboard, a printer, a mouse, and/or one or more monitors—to be connected to the laptop simultaneously by simply connecting the laptop to the docking station. Thus, the user can get access to an external full-sized keyboard, standard mouse, full-size monitor(s), a printer/scanner and a wired network connection when working in the office environment. Ergonomic positioning of the external keyboard and monitor allow the user to assume a more comfortable, neutral posture at the workstation, thus reducing the musculoskeletal stress typically associated with the prolonged use of laptop computers.
In a typical office configuration, the docking station will be located on the work surface to allow the user to easily connect the laptop to the dock. However, while this location provides the convenience of a quick and easy connection to the laptop, the docking station can take up valuable workspace, regardless of whether a vertical stand-alone docking station or a horizontal style docking station is utilized. Moreover, current generation docking stations positioned on the work surface leave the permanent cables exposed on the work surface, creating a cluttered work environment.
SUMMARY
The invention disclosed herein is directed to a computer docking station devised to save desktop space while also eliminating the presence of permanent cables that can clutter the work surface. Whereas prior art computer docking stations typically are unitary units that take up valuable space on the work surface, the computer docking station of the present invention significantly reduces the docking station's desktop footprint by utilizing a split design, with a lower dock subassembly positioned beneath the work surface for housing the permanent cables necessary for the computer workstation to operate, and an upper dock subassembly comprising one or more data ports positioned on top of the work surface. In certain embodiments, a monitor arm mount can also be integrated into the upper dock subassembly, thereby alleviating the need for a separate monitor arm mount without negatively impacting the docking station's footprint. The split-design computer docking station of the present invention provides for improved accessibility to commonly used ports such as universal serial bus (USB) ports, high-speed charging port(s) and audio/microphone ports, while eliminating unsightly permanent cables (e.g., power, video, and network cables) from the desktop, which not only improves aesthetics and the amount of available desk space, but also eliminates the safety hazard of having cables on the work surface and prevents users from intentionally or unintentionally tampering with permanent cables.
The above summary is not intended to describe each illustrated embodiment or every possible implementation. These and other features, aspects, and advantages of the present invention will become better understood with regard to the following description, appended claims, and accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
The accompanying figures, where like reference numerals refer to identical or functionally similar elements throughout the separate views, which are not true to scale, and which, together with the detailed description below, are incorporated in and form part of the specification, serve to illustrate further various embodiments and to explain various principles and advantages in accordance with the present invention:
FIG. 1 is a front perspective view of an embodiment of a computer docking station.
FIG. 2 is a partially exploded view of the embodiment of the computer docking station shown in FIG. 1 .
FIG. 3 is a front perspective view of the embodiment of the computer docking station shown in FIG. 1 wherein the computer docking station is mounted to a table.
FIG. 4 is a rear perspective view of the embodiment of the computer docking station shown in FIG. 1 wherein the computer docking station is mounted to a table.
FIG. 5 is a front perspective view of an embodiment of the upper dock subassembly of the computer docking station shown in FIG. 1 .
FIG. 6 is an exploded view of an embodiment of the upper dock subassembly of the computer docking station shown in FIG. 1 .
FIG. 7 is a front view of an embodiment of the upper dock subassembly of the computer docking station shown in FIG. 1 .
FIG. 8 is a left side view of an embodiment of the upper dock subassembly of the computer docking station shown in FIG. 1 .
FIG. 9 is a right side view of an embodiment of the upper dock subassembly of the computer docking station shown in FIG. 1 .
FIG. 10 is a rear view of an embodiment of the upper dock subassembly of the computer docking station shown in FIG. 1 .
FIG. 11 is a front perspective view of an embodiment of the lower dock subassembly of the computer docking station shown in FIG. 1 .
FIG. 12 is an exploded view of an embodiment of the lower dock subassembly of the computer docking station shown in FIG. 1 .
FIG. 13 is a left side view of an embodiment of the lower dock subassembly of the computer docking station shown in FIG. 1 .
FIG. 14 is a right side view of an embodiment of the lower dock subassembly of the computer docking station shown in FIG. 1 .
FIG. 15 is a rear view of an embodiment of the lower dock subassembly of the computer docking station shown in FIG. 1 .
FIG. 16 is a front view of an embodiment of the lower dock subassembly of the computer docking station shown in FIG. 1 .
FIG. 17 is a from perspective view of the computer docking station shown in FIG. 1 further comprising an embodiment of a cable management system attached to either side of the lower dock subassembly.
FIG. 18 is a partial rear perspective view of the cable management system shown in FIG. 17 .
FIG. 19 is an exploded rear perspective view of the cable management system shown in FIG. 18 .
DETAILED DESCRIPTION
Detailed embodiments of the present invention are disclosed herein; however, it is to be understood that the disclosed embodiments are merely exemplary of the invention, which can be embodied in various forms. Therefore, specific structural and functional details disclosed herein are not to be interpreted as limiting, but merely as a basis for the claims and as a representative basis for teaching one skilled in the art to variously employ the present invention in virtually any appropriately detailed structure. Alternate embodiments may be devised without departing from the spirit or the scope of the invention. Further, the terms and phrases used herein are not intended to be limiting; but rather, to provide an understandable description of the invention. While the specification concludes with claims defining the features of the invention that are regarded as novel, it is believed that the invention will be better understood from a consideration of the following description in conjunction with the drawing figures, in which like reference numerals are carried forward.
As used herein, the terms “a” or “an” are defined as one or more than one. The term “plurality,” as used herein, is defined as two or more than two. The term “another,” as used herein, is defined as at least a second or more. The terms “comprises,” “comprising,” or any other variation thereof are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements, but may include, other elements not expressly listed or inherent to such process, method, article, or apparatus. An element proceeded by “comprises . . . a” does not, without more constraints, preclude the existence of additional identical elements in the process, method, article, or apparatus that comprises the element. The terms “including,” “having,” or “featuring,” as used herein, are defined as comprising (i.e., open language). The term “coupled,” as used herein, is defined as connected, although not necessarily directly, and not necessarily mechanically. As used herein, the term “about” or “approximately” applies to all numeric values, whether or not explicitly indicated. These terms generally refer to a range of numbers that one of skill in the art would consider equivalent to the recited values (i.e., having the same function or result). In many instances these terms may include numbers that are rounded to the nearest significant figure. Relational terms such as first and second, top and bottom, right and left, and the like may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions.
Described now are exemplary embodiments of the present invention. An exemplary embodiment of the computer docking station is depicted in FIGS. 1-19 . Referring to FIGS. 1-5 , the computer docking station 1 can comprise an upper dock subassembly 20 connected to a lower dock subassembly 40 . The upper dock subassembly 20 is designed to house active data port connectors (i.e., frequently connected/disconnected), while the lower dock subassembly 40 is designed to house passive data port connectors (i.e., infrequently connected/disconnected). The upper dock subassembly 20 can include a data port hub 21 , a monitor arm mount 29 , and a bracket 25 . The monitor arm mount 29 is preferably attached or integrated into the top of the data port hub 21 , while the bracket 25 is preferably attached to the rear or bottom of the data port hub 21 . The lower dock subassembly 40 can include a housing 41 , a clamp bracket 42 , and a screw 43 . The housing 41 and clamp bracket 42 can be attached to the bracket 25 of the upper dock subassembly 20 with one or more fasteners. Meanwhile, the screw 43 is threadingly engaged with the clamp bracket 42 . In order to secure the computer docking station 1 to a work surface or table 100 , the user can rotate the screw 43 until the screw's distal end comes into contact with the underside of the work surface 100 . In a preferred embodiment, the housing 41 of the lower dock subassembly 40 is attached to the bracket 25 of the upper dock subassembly 20 with a sufficient space in-between to accommodate a work surface 100 of varying thicknesses.
A variety of alternative mechanisms can be utilized to mount the lower dock subassembly 40 and the upper dock subassembly 20 to the work surface. For example, in a first alternative embodiment, the clamp bracket 42 and screw 43 can be replaced with a fixed bracket that permanently attaches the computer docking station 1 to the work surface, in a second alternative embodiment, the clamp bracket 42 and screw 43 can be replaced with a means for removably mounting the computer docking station 1 to a slat wall. In a third alternative embodiment, the computer docking station 1 can utilize separate brackets to mount the lower dock subassembly 40 and the upper dock subassembly 20 to the work surface, thereby allowing for greater flexibility in mounting locations for each subassembly. In a fourth alternative embodiment, the upper dock subassembly 20 can be secured to the work surface, while the lower dock subassembly 40 is free hanging from a flexible connector to the upper dock subassembly 20 , thereby allowing the user to quickly adjust the positioning of the lower dock subassembly 40 relative to the upper dock subassembly 20 . While FIGS. 1-19 depict the upper and lower dock subassemblies 20 , 40 positioned in a horizontal orientation, one skilled in the art will readily appreciate that either or both of the dock subassemblies 20 , 40 can alternatively be positioned in a vertical orientation.
The active data port connectors of the upper dock subassembly 20 can be linked to the internal components of the lower dock subassembly 40 via one or more bridge cables 6 . In a preferred embodiment, a single bridge cable 6 is utilized to connect the active data port connectors of the upper dock subassembly 20 to the internal components of the lower dock subassembly 40 . In alternative embodiments, multiple bridge cables 6 can be utilized to link the various data ports, or the bridge cable(s) 6 can be replaced with wireless connection.
Referring now to FIGS. 6-10 , the upper dock subassembly 20 can feature a data port hub 21 , a monitor arm mount 29 , a bracket 25 , and one or more data ports 32 - 36 . The data port hub 21 can comprise a hub cover 21 a attached to a hub base 21 c for housing an upper subassembly printed circuit board assembly (PCBA) 22 , while also providing sufficient rigidity to support the weight of one or more monitors attached to the upper dock subassembly 20 . The hub cover 21 a the hub base 21 c , the bracket 25 , and the monitor arm mount 29 can be connected with one or more fasteners 23 , can be molded with snap-fit joints, or can be attached by any other means known in the art. In certain embodiments, a bracket cover 26 can be utilized to secure and hide the one or more bridge cables 6 linking the active data port connectors of the upper dock subassembly 20 to the internal components of the lower dock subassembly 40 .
In the exemplary embodiment depicted in FIGS. 7-10 , the upper subassembly PCBA 22 can feature an indicator light 31 and one or more data ports 32 - 36 . The indicator light 31 functions to provide the user feedback regarding the operation status of the computer docking station 1 . Data port 32 can be an audio combo jack port, while data ports 33 , 34 and 35 preferably are USB-A 3.0 SS (SuperSpeed, 0.9 A) data ports which allow users to connect USB peripherals and mobile devices to the user's laptop via the computer docking station 1 . In an exemplary embodiment, data port 33 is a USB 3.0 BC 1.2 (1.5 A) charging port, while data ports 34 and 35 are USB-C ports capable to be used far both connectivity and power. Data port 36 can comprise a USB 3.0 B-Type upstream connector port designed to be linked to the user's laptop. The USB 3.0 B-Type upstream connector port 36 allows for the transfer of data, video and audio information between the computer and peripherals through the computer docking station 1 , as well as the transfer of power when USB C-Type connector cables are utilized. In alternative embodiments, one skilled in the art will readily acknowledge that the locations and types of data ports 32 - 36 can easily be modified to adapt to changing technologies and uses of the data ports. For example, the back of the data port hub can be used to accommodate one or more of the data ports 32 - 36 . In certain embodiments the upper subassembly PCBA 22 can also feature a wireless charging platform for mobile devices.
Referring now to FIGS. 11-16 , the housing 41 of the lower dock subassembly 40 can comprise a clamp foot 41 a , a top member 41 b and a bottom member 41 c . The clamp foot 41 a is attached to the top member 41 b , while the top member 41 b is attached to the bottom member 41 c to provide a housing for the lower subassembly PCBA 45 . The clamp foot 41 a , the top member 41 b and the bottom member 41 can be connected with one or more fasteners 49 , can be molded with snap-fit joints, or can be attached by any other can known in the art.
In the exemplary embodiment depicted in FIGS. 7-10 , the lower subassembly PCBA 45 features one or more power and data ports 51 - 58 . Data port 51 can comprise a RJ145 100 Mbit Ethernet connector for providing the user's laptop with a wired internet connection through the computer docking station 1 . Data port 52 can comprise a Display Port connector and data port 53 can comprise an HDMI connector for allowing monitor(s) to be connected to the computer docking station 1 . Alternatively, these data port could be a DVI, HDMI or USB-C type connectors/ports. Data ports 54 a - e can be USB-A 3.0 SS (SuperSpeed, 0.9 A) data ports which allow users to connect USB peripherals to the user's laptop via the computer docking station 1 . In alternative embodiments, data ports 54 a - e can be any type of USB port, including but not limited to USB 3.0 BC 1.2 (1.5 A) charging ports and USB-C ports.
Referring now to FIG. 15 , in an exemplary embodiment data port 55 can comprise a DC power connector through which power is supplied to the lower dock subassembly 40 . Data port 56 can comprise USB-A 3.0 SS data bridge cable connector capable of being mated to the bridge cable 6 for transferring data between the upper subassembly PCBA 22 of the upper dock subassembly 20 and the lower subassembly PCBA 45 of the lower dock subassembly 40 . Alternatively, Data port 56 can comprise a USB-C connector or can be replaced with a wireless communication mechanism. Data port 57 can comprise a USB-A mini 3.0 audio combo bridge cable connector or a USB-C port/connector to allow the transfer of audio data between the upper dock subassembly 20 and the lower dock subassembly 40 . Lastly, data port 58 can comprise a DC power bridge cable connector, or alternatively a USB-C connector, for providing power to the upper dock subassembly 20 and attached laptop.
Referring now to FIGS. 17-19 , the computer docking station 1 can further comprise a cable management enclosure 80 attached to either, or both, sides of the lower dock subassembly 40 . The cable management enclosure 80 features an upper cable housing 81 mated with snap joints to a lower lid 82 . The upper housing 81 preferably has three internal hooks allowing the user to wrap any cable slack around the hooks for storage within the cable management enclosure 80 . Adhesive or mechanical-based listening strips 84 (e.g., hook and loop fasteners) can be utilized to secure the upper cable housing 81 to the undersurface of the work surface 100 . The cable management enclosure 80 may also contain an alignment tab 85 for aligning and securing the cable housing 81 to the housing 41 of the lower dock subassembly 40 . A flexible hinge insert 86 can be utilized to releasably connect the lower lid 82 to the cable housing 81 so as to allow a user to access the cable management enclosure 80 by folding down the lower lid 82 .
The foregoing description and accompanying drawings illustrate the principles, exemplary embodiments, and modes of operation of the invention. However, the invention should not be construed as being limited to the particular embodiments discussed above. Many modifications of the embodiments described herein will come to mind to one skilled in the art having the benefit of the teaching presented in the foregoing descriptions and the associated drawings. Accordingly, it should be appreciated that variations to those embodiments can be made by those skilled in the art without departing from the scope of the invention. | A computer docking station devised to save desktop space while also eliminating the presence of permanent cables that can clutter the work surface is disclosed. The computer docking station utilizes a split design, with a lower dock subassembly positioned beneath the work surface for housing the permanent cables necessary for the computer workstation to operate and an upper dock subassembly comprising one or more data ports positioned on top of the work surface. A monitor arm mount can be attached to, or integrated into, the upper dock subassembly, thereby alleviating the need for a separate monitor arm mount without negatively impacting the docking station's footprint. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to fluidic control systems and particularly to systems wherein a monitored pressure or pressure ratio is employed to control a servo valve. More specifically, this invention is directed to servo valves especially suited to use in such control systems and characterized by positive feedback, override capability and hysteresis adjustment. Accordingly, the general objects of the present invention are to provide novel and improved apparatus of such character.
2. Description of the Prior Art
While not limited thereto in its utility, the present invention is particularly well suited for use in a pressure ratio bleed control for a gas turbine engine. As is well known, gas turbine engines may exhibit compressor instability under certain operating conditions. Such instability, also known as compressor surge, occurs when there is a rapid reduction in compressor discharge or burner pressure due to the choking effect of air within the compressor. In order to minimize the effects of compressor surge, it is conventional practice to bleed some of the pressure within the compressor to the ambient atmosphere until such time as the engine passes through the unstable region of its performance characteristic curve.
Prior art pressure ratio bleed controls have provided adaquate performance but have been characterized by a number of disadvantages. Thus, by way of example, the typical prior art control derived a mechanical output from a pneumatic pressure ratio sensor and employed this mechanical output to drive a hydraulic power valve via a gas to liquid converter valve assembly. The necessity of employing a converter valve assembly added to the cost, weight and complexity of the prior art controls while adversely affecting their reliability. Also, prior art pressure ratio bleed controls did not incorporate a simple and convenient override mechanism. A further deficiency of prior art controls was their failure to provide a hysteresis adjustment necessary to compensate for differences in the opening and closing position of the hydraulic valve as commanded by the pneumatic sensor.
SUMMARY OF THE INVENTION
The present invention overcomes the above briefly discussed and other deficiencies and disadvantages of the prior art by providing a novel and improved fluidic control system and a servo valve for use in the system. The control system of the present invention includes a pneumatic sensor unit which provides a mechanical output signal. The mechanical output signal of the pneumatic sensor directly drives a novel hydraulic servo valve assembly. The hydraulic servo valve assembly comprises a servo-operated, differential piston-valve assembly and includes a solenoid operated override mechanism. Also, hysteresis adjustment of the hydraulic valve assembly may be achieved by adjusting the stroke of the differential piston-valve.
BRIEF DESCRIPTION OF THE DRAWING
The present invention may be better understood and its numerous objects and advantages will become apparent to those skilled in the art by reference to the accompanying drawing wherein:
FIG. 1 is a combined orthgonal and schematic view of a preferred embodiment of the invention; and
FIG. 2 is an isolated view of the servo operator 50 of FIG. 1.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The preferred embodiment of the invention comprises a housing which defines a pneumatic sensor subassembly, indicated generally at 10, and a hydraulic valve subassembly, indicated generally at 12. In the manner to be described below, the pneumatic sensor is mechanically coupled to the hydraulic valve subassembly; this coupling being achieved via connecting portion 14 of the control housing. As will also become apparent from the discussion below, the hydraulic valve subassembly 12 is shown with the valve in the closed position.
In view of the utility of the invention in a pressure ratio bleed control, the pneumatic sensor subassembly 10 has been shown as a force balancing pressure ratio responsive device. A pair of sensed pressures, typically ambient or compressor inlet pressure P1 and a pressure P2 proportional to compressor discharge pressure, are applied to respective inlet ports 16 and 18. The pressure P2, which will be higher than pressure P1, is applied directly to the first side of a flexible diaphragm 20 and, via a restricted flow path 22, to the other side of diaphragm 20 and to the first side of a second diaphragm 24. The use of two diaphragms in this fashion is in the interest of safety, in order to provide a device which will continue to be operable in the case of the rupture of one diaphragm, and is in accordance with conventional practice in the art. The diaphragms 20 and 24 are mechanically connected to a lever 26, adjacent a first end thereof, by means which includes a bolt 25. The first end of the lever is spring biased in the downward direction by an adjustable biasing mechanism which includes spring 28 and a movable stop 30 for the spring. The biasing mechanism also includes a temperature compensation device 32 which may, for example, comprise a bimetallic disc. A first lever travel stop 34 is provided adjacent the point of connection between the lever 26 and bolt 25 while the head of bolt 25 defines a stop for movement away from stop 34.
The opposite end of lever 26 is supported by an evacuated bellows 36 which establishes a P1 pressure reference. A lever ratio slope adjustment device 38 is provided at the point of connection between lever 26 and bellows 36. Intermediate its length lever 26 is pinned to an output shaft 40 which extends through housing portion 14. For convenience of illustration, shaft 40 has been shown extending downwardly at an angle to lever 26. As will be obvious to those skilled in the art, in actual practice shaft 40 provides a fixed fulcrum upon which lever 26 pivots and thus shaft 40 will be oriented perpendicularly to the plane of pivoting movement of lever 26.
Should P1 decrease with respect to P2, the forces produced by the resultant pressure differential across the diaphragms 20 and 24 will result in upward movement thereof against the bias of spring 28 and consequently in the counter-clockwise rotation of output shaft 40. Conversely, a decrease in the P1/P2 ratio will result in clockwise rotation of shaft 40. As will become apparent from the discussion below, the control is a snap-action device whereby a power valve will be opened when a preselected P1/P2 ratio is exceeded and the power valve will be closed when a second, and usually lower, P1/P2 curve is passed as the pressure ratio decreases. The device has been shown in a condition where the P1/P2 ratio has increased to the power valve opening threshold.
Within housing portion 14 shaft 40 passes through a rotating seal, indicated generally at 42, which provides isolation between the gaseous environment within the pneumatic sensor subassembly 10 and the liquid environment within the hydraulic valve subassembly 12. A drain port 44 communicates with seal 42 to provide for bleeding off any hydraulic fluid which leaks past the initial shaft seals and into the interior of the sealing means.
Within the portion of the housing which defines the hydraulic valve subassembly, the second end of output shaft 14 is connected to a lever and clamp mechanism 46 which transmits the rotating motion of shaft 40 to a servo operator indicated generally at 50; servo operator 50 and lever 26 thus pivoting in unison about the axis of shaft 40. With a P2/P1 pressure ratio below the threshold value as depicted, the shaft 40 generates a clockwise torque. This torque is applied to servo operator 50. The output shaft 52 of the servo operator controls the position of a disc 54 which in part defines a servo valve. When clockwise torque is generated by the pneumatic sensor, the servo valve is driven to the closed position wherein the disc 54 is in contact with the end of differential piston-power valve member 60. The servo operator 50 includes a spring loaded overtravel mechanism as shown.
As noted, the hydraulic valve subassembly also includes an output or power valve member 60 in the form of a differential piston. In addition, the valve subassembly comprises inlet port 62, bleed port 64 and a discharge port 66; port 66 being connected to a load. The load will typically be a hydraulically operated compressor bleed valve assembly. The working fluid for the hydraulic valve subassembly of the present invention will, in the environment of a pressure ratio bleed control, typically be the pressurized fuel for the engine; liquid at a relatively high pressure, on the order of 1000 psi, being applied to port 62 and port 64 being maintained at a lower pressure, typically on the order of 150 psi.
With the servo valve closed as shown the high pressure fluid at inlet port 62 will be applied, via a servo flow control orifice 68, to the large end of the output valve member 60. Member 60 is provided with a pressure relief passage 70 therethrough which, with the servo valve closed, is sealed by disc 54. Accordingly, with the servo valve closed, member 60 will be unbalanced in the closed position. Valve member 60 will thus be hydraulically urged toward servo valve 54, and, through the action of the servo operator overtravel mechanism, against a cooperating sealing surface 69 internally of the housing. Although not shown in such condition, the servo operator mechanism will be overtraveled at this time as shown in FIG. 1 and communication between supply port 62 and discharge port 66 will be prevented. FIG. 2 depicts servo operator 50 in the position it would take, for example, during movement of shaft 52 away from servo valve disc 54.
Should the P2/P1 pressure ratio increase above the preset threshold, shaft 40 will rotate thereby generating a counterclockwise torque which will withdraw the servo operator shaft 52 from disc 54. As the servo valve flow area at the end of member 60 increases, disc 54 being moved to the left under the influence of pressure to uncover port 72, it approaches the magnitude of the flow area of flow control orifice 68. The opening of the servo valve permits bleeding down of the pressure acting on the large end of valve member 60 to the level of the pressure applied to inlet port 64. When the pressure at the large end of valve member 60 declines sufficiently, the valve will become unbalanced toward the open position through the action of the high pressure fluid on shoulder 74 of member 60. Valve member 60 will thus begin to move. During the first motion of output valve member 60 the servo opening is correspondingly increased and the output valve becomes increasingly unbalanced toward the open position. This results in a snap-action opening of valve 60 thereby establishing communication between inlet port 62 and discharge port 66.
Should the P2/P1 ratio decrease, a counterclockwise torque will be developed as a result of the movement of shaft 40 and the servo operator output shaft 52 will move toward servo valve disc 54. Movement of disc 54 to the right, considering the embodiment shown, will result in decreasing the servo opening and the pressure at the large end of output valve member 60 will begin to build up. When the pressure differential across the output valve piston becomes sufficiently high the valve will become unbalanced in the closed direction causing a snap-action closing of the valve to the position shown. The closing P1/P2 ratio will be lower than the opening ratio, due to inherent hysteresis of the system, and means must be provided to compensate for this hysteresis. The compensation means of the present invention will be discussed below.
The hydraulic control valve subassembly of the present invention also includes an override mechanism indicated generally at 80. Override mechanism 80 comprises a solenoid 82 which operates a plunger mechanism 84; the plunger mechanism also being provided with an overtravel device as shown. The solenoid 82 can be energized at any time, for example during a gas turbine engine thrust reversal mode, whereby the output shaft of the plunger mechanism 84 will contact the servo operator output shaft 52 forcing the servo operator toward the servo valve 54 thereby causing the servo valve to close. The closing of the servo valve will, in the manner described above, result in the closing of the power valve 60.
As will be obvious from the description above, the stroke of the output valve member 60 results in a difference in servo operator position for opening and for closing the output valve. As previously discussed, this position difference is realized as a P2-P1 opening and closing ratio difference at the computing end of a pressure ratio bleed control and appears as hysteresis. This hysteresis is proportional to output valve travel and is adjustable in magnitude by means of a valve travel stop adjustment 90 which limits the movement of member 60 to a very short stroke.
While a preferred embodiment has been shown and described, various modifications and substitutions may be made thereto without departing from the spirit and scope of the invention. Thus, by way of example, the pneumatic subassembly 10 of the invention may take the form of a pressure sensor rather than a differential pressure responsive device. Accordingly, it is to be understood that the present invention has been described by way of illustration and not limitation. | A hydraulic servo valve assembly and a control system therefor employing a pneumatic sensor-actuator are disclosed. The servo valve assembly comprises a servo-operated power valve assembly including a differential piston, a solenoid operated override and hysteresis adjustment. The valve assembly is a "snap-action" device wherein the power valve differential piston is selectively positioned through use of the pneumatic sensor controlled servo valve to vent the pressure applied to the larger area reaction surface of the piston. | 5 |
CROSS-REFERENCE TO RELATED PATENT APPLICATIONS
[0001] This application is a divisional of application Ser. No. 11/223,141, filed Sep. 12, 2005, now pending, the entire contents of which are incorporated herein by reference. This application claims only subject matter disclosed in the parent application and therefore presents no new matter.
BACKGROUND OF THE INVENTION
[0002] This invention relates to a bonding apparatus for plastic members or the like in the electronic component manufacturing field requiring highly clean environment and materials in the manufacture. More specifically, this invention relates to a thermal fusion-bonding apparatus and fusion-bonding method for melting and bonding members by applying heat thereto and a resin member fusion-bonded thereby, for use in the execution of pure water or ultrapure water conveyance piping.
[0003] In recent years, following the miniaturization, advanced functionality and increased performance of products in the semiconductor and liquid-crystal display manufacturing fields, what are extremely highly purified have been required with respect also to utilities used in the manufacture. For example, the quality of ultrapure water or the like has been required to be extremely highly pure, wherein the total amount of impurities allowed to be present in the water is in the order of ppb (one millionth) to ppt (one trillionth). Particularly, the allowable amount of metal impurities in the water has started to shift from the order of ppt to the order of ppq (one 1000-trillionth). On the other hand, the allowable amount of organic matter (TOC: total organic carbon) in the water is still in the order of ppb and thus the allowable value thereof is higher than the other impurities. In these circumstances, purification of members to be used has been developed as an attempt to reduce the TOC amount in the water. This is well exemplified by clean PVC (clean polyvinyl chloride), fluororesin-based PVDF (polyvinylidene fluoride), or the like used in ultrapure water piping or the like, which is cleaner than general-purpose PVC piping.
[0004] In the execution of piping, an adhesive or the like has conventionally been used for bonding. However, since elution of organic matter from the adhesive has arisen as a problem, thermal fusion-bonding apparatuses have often been used. The thermal fusion-bonding apparatus employs a method of heating a bonding portion to near the melting point of bonding members, thereby melting and bonding the members.
[0005] In the method of raising the temperature to near the melting point to carry out the fusion bonding at the time of bonding the resin members as described above, the resin forming the piping reacts with oxygen and moisture in the atmosphere so that oxidative degradation, decomposition/dissociation, or the like of the resin material is already generated at the fusion-bonding portion. This bonded portion is one of causes for elution of TOC components into the ultrapure water.
[0006] Japanese Unexamined Patent Application Publication (JP-A) No. H8-285166 (patent document 1) proposes a pipe header which is usable for piping capable of transporting even ultrapure water. This pipe header comprises a main pipe in the form of a thermoplastic resin pipe and branch pipes connected to the main pipe. Each branch pipe is in the form of a short pipe with a curved flange and the curved flange is fusion-bonded along the outer periphery of the thermoplastic resin pipe.
[0007] As described above, the thermal fusion-bonding method in the atmosphere-open state cannot avoid the elution of the TOC components into the water due to the degradation of the fusion-bonded portion. Therefore, there has arisen a problem that the TOC amount in the ultrapure water is not easily reduced immediately after the execution of the piping and it is necessary to let the water run for days in order to guarantee the quality of the water and to continue it until the eluted organic matter (TOC components) is exhausted.
[0008] On the other hand, as a result of assiduous studies by the inventors of this invention, it has been found out that the degradation of the resin forming the piping, which occurs in the thermal fusion bonding, is caused by oxygen and moisture in the atmosphere.
[0009] It has become clear that, for reducing the elution from the fusion-bonded portion and enhancing the bonding strength, it is necessary to carry out the bonding after controlling the oxygen concentration in the bonding environment and sufficiently removing adsorbed moisture on the surface of the bonding portion immediately before the bonding. Further, it has become clear that, for realizing the low oxygen concentration environment and the low moisture concentration environment, it is necessary to cover a fusion-bonding apparatus with a member having low permeability to gas and moisture to thereby isolate it from the external environment and let the gas flow there and, not only to reduce the oxygen and moisture amount contained in the flowing supply gas but also to form the surface inside the apparatus serving as a flow path for the gas to be an inactive surface where the moisture is difficult to be adsorbed.
[0010] On the other hand, patent document 1 does not identify any issues raised when bonding the ultrapure water conveyance pipes.
SUMMARY OF THE INVENTION
[0011] It is therefore an object of this invention to provide an atmosphere-controlled thermal fusion-bonding apparatus and fusion-bonding method capable of bonding resin members without changing the quality of a bonded portion, where the resin members are melted and bonded together by the application of heat, free of oxidative degradation or the like and thus while maintaining the original properties possessed by the members.
[0012] It is another object of this invention to provide a resin member bonded by the foregoing thermal fusion-bonding apparatus or fusion-bonding method.
[0013] A bonding apparatus provided by this invention is a bonding apparatus that applies heat to bonding resin members to thereby melt and bond them and is characterized in that a bonding portion is covered and the oxygen concentration and the moisture concentration of a bonding atmosphere are lower as compared with the oxygen concentration and the moisture concentration of an atmosphere outside the apparatus and in that the oxygen concentration is 1 vol % or less and the moisture concentration is 0.1 vol % or less in the bonding environment at the bonding portion. Preferably, the oxygen concentration is 100 vol ppm or less and the moisture concentration is 100 vol ppm or less in the bonding environment and, more preferably, the oxygen concentration is 1 vol ppm or less and the moisture concentration is 1 vol ppm or less.
[0014] A heating method of the bonding apparatus provided by this invention for heating the bonding portion is not limited to particular means, but is preferably one of a heater and a laser.
[0015] The bonding apparatus of this invention is characterized in that at least the bonding portion is supplied with a low dew point gas. The bonding apparatus has a supply port for supplying the low dew point gas from the exterior of the apparatus and an exhaust port. It is preferable that the oxygen content of the low dew point gas at the supply port be 100 vol ppm or less and the moisture content thereof be 100 vol ppm or less.
[0016] A pipe for supplying the low dew point gas is also not limited to particular means. However, in order to supply the gas with the oxygen content of 100 vol ppm or less and the moisture content of 100 vol ppm or less to the bonding portion, it is preferably at least one of an electrolytically polished stainless surface, an electrochemically polished stainless surface, an electrolytically polished or electrochemically polished surface containing a chromium oxide as a main component, and an electrolytically polished or electrochemically polished surface containing an aluminum oxide as a main component.
[0017] In the bonding apparatus of this invention, the low dew point gas is characterized by containing at least one of nitrogen, helium, neon, argon, krypton, xenon, and hydrogen. Although nitrogen, helium, neon, argon, krypton, xenon, hydrogen, or the like is cited as an example of the foregoing gas, these may be mixed for use. In terms of suppressing oxidation of the bonding portion, it is preferable to mix hydrogen at 0.1 vol % or more.
[0018] A material, covering the bonding portion, of the bonding apparatus of this invention is not particularly limited as long as the environment can be ensured wherein the oxygen concentration is 1 vol % or less and the moisture concentration is 0.1 vol % or less. It is preferably at least one of an electrolytically polished stainless surface, an electrochemically polished stainless surface, an electrolytically polished or electrochemically polished surface containing a chromium oxide as a main component, and an electrolytically polished or electrochemically polished surface containing an aluminum oxide as a main component.
[0019] Further, the bonding apparatus of this invention is characterized by comprising a mechanism for reducing the oxygen concentration to 1 vol % or less and the moisture concentration to 0.1 vol % or less at the bonding portion. As means for reducing the oxygen concentration and the moisture concentration to 1 vol % or less at the bonding portion, there is cited a method of supplying a gas with a low oxygen concentration and a low dew point. Further, by repeating the gas supply and decompression at the bonding portion, it is possible to reduce the oxygen concentration to 1 vol % or less and the moisture concentration to 0.1 vol % or less more quickly, which is thus more preferable. The bonding may be carried out while supplying the gas or in the state where the supply is stopped.
[0020] The bonding apparatus of this invention is characterized by comprising meters for measuring the oxygen concentration and the moisture concentration inside the apparatus. As means for measuring the oxygen concentration, it is preferable to use one of an oxygen analyzer and a gas chromatograph. As means for measuring the moisture concentration, it is preferable to use one of a dew point meter, an infrared spectrometer, and an atmospheric pressure ionization mass spectrometer (API-MS).
[0021] A resin member bonding method of this invention is a method of applying heat to resin members to thereby melt and bond them. The bonding resin members are not particularly limited, but each may be a hydrocarbon-based member that preferably contains, for example, at least one of resins of vinyl chloride (PVC), cycloolefin polymer (COP), polypropylene (PP), polyethylene (PE), and polyetheretherketone (PEEK). On the other hand, it may be a fluorocarbon-based member that preferably contains, for example, at least one of resins of polyvinylidene fluoride (PVDF), tetrafluoroethylene (PTFE), perfluoroalkoxylvinylether (PFA), tetrafluoroethylene-hexafluoropropylene copolymer (FEP), tetrafluoroethylene-ethylene copolymer (ETFE), and vinyl fluoride (PVF).
[0022] It is preferable that the resin members be bonded together by the use of the apparatus provided by this invention wherein the resin is heated and melted after reducing the oxygen concentration to 1 vol % or less and the moisture concentration to 0.1 vol % or less in the bonding environment at the bonding portion, thereby carrying out the bonding.
[0023] The bonding apparatus of this invention is capable of controlling the oxygen concentration and the moisture concentration in the atmosphere at the bonding portion to be lower as compared with those in the atmosphere outside the apparatus so that it is possible to implement thermal fusion bonding without degradation of the bonding resin members. Consequently, it becomes possible to reduce the elution from a bonded resin member and, further, by using the resin member obtained by the present apparatus or method in the execution of ultrapure water supply piping, it is possible to achieve the TOC water quality of ultrapure water in a significantly shorter time than conventional.
BRIEF DESCRIPTION OF THE DRAWING
[0024] FIG. 1 is a schematic diagram showing a bonding apparatus and an evaluation apparatus for evaluating bonding implemented by the bonding apparatus;
[0025] FIG. 2 is a graph showing the results of evaluating bonding by the use of the evaluation apparatus shown in FIG. 1 and, herein, showing a change in COP thermal decomposition temperature according to a change in oxygen concentration in a bonding portion cover;
[0026] FIG. 3 is a graph showing the results of evaluating bonding by the use of the evaluation apparatus shown in FIG. 1 and, herein, showing a change in COP thermal decomposition temperature according to a change in moisture concentration in the bonding portion cover;
[0027] FIG. 4 is a schematic diagram showing a bonding apparatus and an evaluation apparatus for measuring an elution amount in a pipe thermally fusion-bonded by the bonding apparatus; and
[0028] FIG. 5 is a diagram showing an elution amount evaluation state for evaluating the elution amount of the fusion-bonded clean PVC pipe.
DESCRIPTION OF THE PREFERRED EMBODIMENT
[0029] Hereinbelow, examples of this invention will be described. As a matter of course, this invention is not to be limited to the following examples.
[0030] The analysis conditions in the following examples and comparative examples are as follows.
(Analysis Condition 1)
[0031] Fourier Transform Infrared Spectroscopic Analysis (hereinafter abbreviated as “FT-IR analysis”)
Apparatus: FTS-50A manufactured by Bio-Rad Laboratories, Inc.
(Analysis Condition 2)
[0032] Atmospheric Pressure Ionization Mass Spectrometry (hereinafter abbreviated as “API-MS analysis”)
Apparatus: UG-400 manufactured by Renesas Technology Corp.
(Analysis Condition 3)
[0033] Total Organic Carbon Analysis (hereinafter abbreviated as “TOC analysis”)
Apparatus: O•I-1010 (Wet Oxidation Method) manufactured by O•I Corporation
Example 1
[0034] An evaluation apparatus in Example 1 will be described with reference to FIG. 1 .
[0035] In FIG. 1 , 1 denotes an inert gas supply source, 2 an inert gas supply pipe, 3 a bonding portion cover, 4 a bonding portion heater, 5 a bonding portion, 6 a heater power supply, 7 and 8 bonding pipes, 9 and 10 pipe sealing covers each with an orifice, 11 an oxygen bomb, 12 a mass flow controller, 13 a moisture generator, 14 an adjustment valve, 15 and 16 flow rate adjusting valves, 17 an FT-IR, and 18 an API-MS.
[0036] FIG. 1 is a schematic diagram of the apparatus capable of evaluating thermal decomposition characteristics of a resin, wherein the bonding pipe 7 and the bonding pipe 8 are bonded at the bonding portion 5 . This evaluation apparatus comprises the bonding portion cover 3 hermetically covering the bonding portion including the heater 4 for heating the bonding portion 5 and the bonding portion 5 , and the heater power supply 6 . There are provided a mechanism ( 1 to 10 ) for reducing the oxygen concentration and the moisture concentration in an atmosphere of the bonding portion, a mechanism ( 11 to 14 ) for adjusting the oxygen concentration and the moisture concentration in the atmosphere of the bonding portion, and a mechanism ( 15 to 18 ) for measuring the oxygen concentration and the moisture concentration in the atmosphere of the bonding portion.
[0037] In this example, high-purity Ar was used as an inert gas for controlling the atmosphere and supplied at 1 L/min. As the gas supply pipe 2 for supplying the inert gas, use was made of a pipe of which the inner surface was subjected to electrochemical polishing and then applied with a chromium oxide treatment.
[0038] As the cover 3 covering the bonding portion 5 for controlling the bonding portion 5 in a low oxygen atmosphere and a low moisture concentration atmosphere, use was made of a container formed of a cycloolefin polymer (COP) (ZEONOR 1060 manufactured by ZEON Corporation) being a hydrocarbon-based resin made of carbon and hydrogen.
[0039] The API-MS 18 was disposed midway in an exhaust passage for the gas supplied to the bonding portion 5 , thereby managing the moisture concentration (in the order of ppm) and the oxygen concentration. Further, the FT-IR 17 was disposed to examine the moisture concentration (in the order of %) and thermal decomposition characteristics of the bonding resin members.
[0040] In this example, bonding was carried out by the use of the pipes 7 and 8 containing as a main component the foregoing ZEONOR 1060 being the COP and each having a length of 1 m. On the sides, opposite to the bonding portion 5 , of the pipes 7 and 8 , the pipe sealing covers 9 and 10 each having the orifice connected thereto were attached, respectively, for preventing back diffusion from the exterior.
[0041] The atmosphere inside the bonding portion cover 3 was Ar and, when thermal fusion bonding was implemented in a system where the oxygen concentration inside the bonding portion cover 3 was controlled at 1 vol %, the COP thermal decomposition temperature was 220 to 230° C. The results are shown in FIG. 2 .
Example 2
[0042] By the use of the evaluation apparatus of Example 1, when thermal fusion bonding was implemented in a system where the oxygen concentration inside the bonding portion cover 3 was controlled at 100 vol ppm, the COP thermal decomposition temperature was 260 to 270° C. The results are shown in FIG. 2 .
Example 3
[0043] By the use of the evaluation apparatus of Example 1, when thermal fusion bonding was implemented in a system where the oxygen concentration inside the bonding portion cover 3 was controlled at 1 vol ppm, the COP thermal decomposition temperature was 300 to 310° C. The results are shown in FIG. 2 .
Example 4
[0044] By the use of the evaluation apparatus of Example 1, when thermal fusion bonding was implemented in a system where the inert gas was supplied to the inside of the bonding portion cover 3 in advance and the inside of the bonding portion cover 3 was controlled in an oxygen-free state (<1 vol ppb), the COP thermal decomposition temperature was 300 to 310° C. The results are shown in FIG. 3 .
Example 5
[0045] By the use of the evaluation apparatus of Example 1, when thermal fusion bonding was implemented in a system where the inert gas was supplied to the inside of the bonding portion cover 3 in advance and the inside of the bonding portion cover 3 was controlled in an oxygen-free state (<1 vol ppb) and where the moisture concentration inside the bonding portion cover 3 was controlled at 0.1 vol %, the COP thermal decomposition temperature was 200 to 210° C. The results are shown in FIG. 3 .
Example 6
[0046] By the use of the evaluation apparatus of Example 1, when thermal fusion bonding was implemented in a system where the inert gas was supplied to the inside of the bonding portion cover 3 in advance and the inside of the bonding portion cover 3 was controlled in an oxygen-free state (<1 vol ppb) and where the moisture concentration inside the bonding portion cover 3 was controlled at 1 vol ppm, the COP thermal decomposition temperature was 300 to 310° C. The results are shown in FIG. 3 .
Comparative Example 1
[0047] By the use of the evaluation apparatus of Example 1, when thermal fusion bonding was implemented in the state where the bonding portion 5 was open to the atmosphere, the COP thermal decomposition temperature was 150 to 160° C. The results are shown in FIG. 2 .
Comparative Example 2
[0048] By the use of the evaluation apparatus of Example 1, when bonding was implemented in a system where the inert gas was supplied to the inside of the bonding portion cover 3 in advance and the inside of the bonding portion cover 3 was controlled in an oxygen-free state (<1 vol ppb) and where the moisture concentration inside the bonding portion cover 3 was controlled at 1.5 vol %, the COP thermal decomposition temperature was 120 to 130° C. The results are shown in FIG. 3 .
[0049] In this comparative example, in order to confirm the influence exerted on the resin decomposition properties only by the moisture concentration, the evaluation was performed by setting the moisture concentration inside the bonding portion cover 3 to be 1.5 vol % while controlling the oxygen concentration inside the bonding portion cover 3 to be less than 1 vol ppb. This moisture concentration of 1.5 vol % is equivalent to the moisture concentration in the atmosphere-open state.
[0050] It can be confirmed from FIGS. 2 and 3 that the thermal decomposition temperature is shifted according to the oxygen concentration and the moisture concentration inside the bonding portion cover 3 . That is, it is shown that the thermal decomposition of the bonding resin pipes 7 and 8 can be suppressed by controlling the oxygen concentration and the moisture concentration inside the bonding portion cover 3 . It is seen that when the oxygen concentration inside the bonding portion cover 3 exceeds 1 vol %, the COP resin members are significantly degraded in a low-temperature region. The occurrence of the thermal decomposition in the low-temperature region means that the degradation of the resin members occurs during melting and bonding (during thermal fusion bonding), and the thermally decomposed resin members easily release organic matter. Therefore, the oxygen concentration inside the bonding portion cover 3 is preferably 1 vol % or less, and more preferably 100 vol ppm or less. It is further preferably 1 vol ppm or less.
[0051] Further, it is seen that when the moisture concentration exceeds 0.1 vol %, the resin members are significantly degraded in a low-temperature region. The moisture concentration also needs to be controlled like the oxygen concentration. Therefore, the moisture concentration inside the bonding portion cover 3 is preferably 0.1 vol % or less, and more preferably 1 vol ppm or less.
Example 7
[0052] An elution amount evaluation was implemented with respect to a clean PVC pipe that was thermally fusion-bonded by the use of an atmosphere-controlled bonding (thermal fusion-bonding) apparatus shown in FIG. 4 . The same numerals are assigned to constituent portions that are the same as those ( 1 to 10 ) in FIG. 1 . What are newly added when constituting the apparatus are indicated as 19 to 26 . 19 denotes a flow rate adjusting valve, 20 a check valve, 21 and 22 flow rate adjusting valves, 23 an oxygen analyzer, 24 a moisture analyzer, and 25 and 26 orifices.
[0053] As bonding pipes 7 and 8 , use was made of an ESLON super clean pipe (clean PVC base material) (Φ 1 inch, 2 m) manufactured by Sekisui Chemical Co., Ltd. Thermal fusion bonding was performed at 10 portions in an atmosphere inside a bonding portion cover 3 where the oxygen concentration and the moisture concentration were each controlled at 1 vol ppm. As shown in FIG. 5 , the thermally fusion-bonded resin (clean PVC) pipe was filled with ultrapure water and sealed, and the water inside was left standing for three days and then taken out, thereby performing a TOC (water quality) analysis thereof. As the water used in the evaluation, use was made of ultrapure water having a TOC concentration of less than 0.5 μm/L, manufactured by Tohoku University's Future Information Industry Creation Center.
[0054] As a result of an analysis by the use of O•I-1010 (Wet Oxidation Method) manufactured by O•I Corporation, the TOC concentration was 0.7 μg/L.
[0055] The analysis results are shown in Table 1.
[0000]
TABLE 1
TOC Elution Amount Evaluation Result
Thermally Fusion-Bonded Portions (10 Portions in Total)
Atmosphere-Open Thermal Fusion Bonding
Atmosphere-Controlled Thermal Fusion Bonding
(Oxygen Concentration: 20% ·
(Oxygen Concentration: 1 ppm ·
Moisture Concentration: 1.5%)
Moisture Concentration: 1 ppm)
TOC Concentration
6.9
0.7
after 3 Days from
Filling of Water (μg/L)
Ultrapure Water TOC Concentration: <0.5 μg/L
Comparative Example 3
[0056] Thermal fusion bonding was carried out like in Example 6 except that the bonding portion cover 3 was opened to provide an atmosphere-open condition (oxygen concentration 20 vol %, moisture concentration 1.5 vol %). As a result of an analysis by the use of the analysis apparatus shown in Example 7, the TOC concentration was 6.9 μg/L. The analysis results are shown in the table.
[0057] As confirmable also from the table, it has been confirmed that the elution amount from the resin pipe thermally fusion-bonded in the atmosphere-open state with the bonding portion cover 3 being open is 6.9 μg/L in this example, while, the elution amount from the resin pipe thermally fusion-bonded in the state where the oxygen concentration and the moisture concentration in the atmosphere inside the bonding portion cover 3 are each controlled at 1 vol ppm is 0.7 μg/L, thus, there is about 10 times difference. That is, it has been demonstrated that, from resin members thermally fusion-bonded by the resin bonding apparatus or bonding method according to this invention, a new bonded resin member with small elution of TOC components can be supplied.
[0058] The bonding apparatus and bonding method of this invention are used as a bonding apparatus and bonding method when manufacturing ultrapure water supply pipes or other liquid or gas resin pipes, or resin members that contact a liquid or gas, in the electronic industry field such as in a semiconductor or liquid-crystal display plant that requires ultrapure water, gases, chemical liquids, and so on. | By performing thermal fusion bonding in the state where a bonding portion is covered with a bonding portion cover and the concentrations of oxygen and moisture inside the bonding portion cover are set lower than the concentrations of oxygen and moisture in the atmosphere, it is possible to reduce elution from a bonded resin-based pipe. | 1 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application is a divisional of U.S. patent application Ser. No. 14/191,939, filed Feb. 27, 2014 and entitled “Temperature Stable MEMS Resonator,” which is a divisional of U.S. patent application Ser. No. 13/562,684, filed Jul. 31, 2012 and entitled “Method of Manufacturing a Microelectromechanical System (MEMS) Resonator” (now U.S. Pat. No. 8,667,665), which is a divisional of U.S. patent application Ser. No. 11/963,709, filed Dec. 21, 2007 and entitled “Method for Fabricating a Microelectromechanical System (MEMS) Resonator” (now U.S. Pat. No. 8,234,774). Each of the foregoing applications is hereby incorporated by reference herein in its entirety.
TECHNICAL FIELD
Embodiments of the present invention relate generally to temperature compensated microelectromechanical systems (MEMS) oscillators and, more specifically, to a temperature stable MEMS resonator.
BACKGROUND
Many electronic devices include a real-time clock that runs continuously so that accurate time and date information, among other things, may always be maintained. Oscillators are commonly used in the timing circuitry of hand-held and portable electronic devices, such as wrist watches and cell phones. A typical oscillator circuit includes a resonator and an associated drive circuit to drive the resonator. Quartz is often used for the resonator. However, with the continuous push to decrease the size of electronic circuits, MEMS resonators fabricated from silicon are expected to replace quartz resonators in various oscillator circuit designs.
A major obstacle, though, to implementing MEMS resonators is that the mechanical properties of some MEMS resonator materials are dependent on temperature. Material stiffness is one example of a mechanical property that is dependent on the temperature. The temperature dependence of the material stiffness may be described with the temperature coefficient of stiffness, also known as temperature coefficient of Young's Modulus (TCE). As a result of the temperature dependence of the mechanical properties of MEMS resonator materials, properties of MEMS resonators (e.g., resonant frequency) may also exhibit temperature dependence. For example, a thermal coefficient of frequency (TCF) of a MEMS resonator, derived from the design of the resonator and the material properties of the one or more materials that make up the resonator, may be 30 ppm/° C., which means that if the MEMS resonator normally oscillates at a frequency of 1 MHz, then a 1° C. change in temperature results in a 30 Hz frequency shift. For some applications, the TCF of the resonator should be less than 1 ppm/° C. Consequently, many MEMS oscillator circuits require some form of temperature compensation to maintain the frequency of the signal produced by the MEMS resonator (referred to herein as the “output signal”) at a target value defined by a particular application.
One way to address the temperature dependence of MEMS resonator materials is to employ additional electronic circuits that periodically adjust the frequency of the output signal to maintain the frequency at the target value despite temperature fluctuations within the system. However, temperature-compensation electronic circuits are complicated to design and implement, take up valuable chip area, add to the overall chip cost, increase total test time, and consume significant amounts of power.
Another way to address the temperature dependence of MEMS resonator materials is to decrease the magnitude of the TCF of the MEMS resonator by oxidizing the surface of the MEMS resonator beams. As is well-known, some oxides become stiffer at higher temperatures, thereby counteracting the behavior of the MEMS resonator material over temperature. The addition of oxide may reduce the magnitude of the TCF of the MEMS resonator to nearly 0 ppm/° C. This approach, however, has several major drawbacks.
One drawback is related to process control. The TCF of a MEMS resonator coated with oxide is dependent on the thickness of the oxide on its surface. However, in a manufacturing environment, controlling oxide growth to better than 10% may be challenging, making TCF control via oxide coating difficult as well. Another drawback is that the oxide layer may accumulate electrical charge on the surface. Charge build-up on the surface of a MEMS resonator may cause the frequency of the resonator to drift over time. Yet another drawback arises from design limitations inherent in MEMS resonator systems. In order to counteract the behavior of MEMS resonator materials, a sufficient amount of oxide should be grown on the MEMS resonator beams. However, a thick layer of oxide requires a longer deposition time and increases the risk of stress-induced cracking, especially during or after an annealing step. In addition, large amounts of oxide may cause the stress in the MEMS resonator beams to become poorly controlled, adding uncertainty to its desired resonant frequency. Finally, a thick oxide layer may bridge or nearly bridge the gap between the MEMS resonator beams and their corresponding electrodes, leading to device failure. For example, if a MEMS resonator beam is 20 μm wide, and there is a gap of 0.7 μm between the beam and the electrodes, growing the 1.5-2 um of oxide necessary to reduce the TCF of the MEMS resonator is not possible.
As the foregoing illustrates, what is needed in the art is a better way to decrease the TCF of a MEMS resonator.
SUMMARY OF ONE OF MULTIPLE DISCLOSED EMBODIMENTS
One embodiment of the present invention sets forth a method for fabricating a microelectromechanical system (MEMS) resonator having a reduced thermal coefficient of frequency (TCF). The method includes the steps of defining one or more slots within the MEMS resonator, fabricating the one or more slots, and filling the one or more slots with oxide.
One advantage of the disclosed method is that by growing or depositing oxide within the slots, the amount of oxide growth or deposition on the outside surfaces of the MEMS resonator may be reduced. As a result, the TCF of the MEMS resonator may be changed in a manner that is beneficial relative to prior art approaches.
BRIEF DESCRIPTION OF THE DRAWINGS
So that the manner in which the above recited features of the present invention can be understood in detail, a more particular description of the invention, briefly summarized above, may be had by reference to embodiments, some of 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. 1A is a conceptual diagram of a MEMS resonator, according to one embodiment of the present invention;
FIG. 1B illustrates a cross-section of the MEMS resonator beam of FIG. 1A , according to one embodiment of the present invention;
FIG. 2 is a conceptual diagram of a MEMS resonator, according to another embodiment of the present invention;
FIGS. 3A through 3D illustrate the process of filling slots within a MEMS resonator with oxide, according to one embodiment of the present invention;
FIG. 4A illustrates the effects of placing slots filled with oxide in areas of high strain concentration on the TCF of a MEMS resonator, according to one embodiment of the present invention;
FIG. 4B is a magnified view of the area of FIG. 4A where the TCF of a MEMS resonator with slots is within 1 ppm/° C.;
FIG. 5 sets forth a flow diagram of method steps for filling slots within a MEMS resonator with oxide, according to another embodiment of the present invention;
FIGS. 6A through 6E illustrate the process of completely filling the slots within the MEMS resonator of FIG. 2 with oxide, according to the method steps of FIG. 5 ;
FIGS. 7A through 7E illustrate the process of partially filling the slots within the MEMS resonator of FIG. 2 with oxide, according to the method steps of FIG. 5 ;
FIG. 8 is a conceptual diagram of an extensional resonator, according to one embodiment of the present invention;
FIG. 9 is a conceptual diagram of an electronic device configured to implement one or more aspects of the present invention; and
FIGS. 10A through 10E illustrate different ways to position a MEMS resonator, a drive circuit, and application circuitry on one or more substrates.
DETAILED DESCRIPTION
FIG. 1A is a conceptual diagram of a MEMS resonator 100 , according to one embodiment of the present invention. As shown, the MEMS resonator 100 includes a MEMS resonator anchor 116 that fixes a base 118 of the MEMS resonator 100 to an underlying handle wafer (not shown). The MEMS resonator 100 further includes MEMS resonator beams 112 and 114 of length L that are mechanically coupled to the base 118 . By applying a time-varying signal to drive electrodes (not shown) at a given frequency and, optionally, a DC voltage between the MEMS resonator 100 and the drive electrodes, electrostatic forces are generated that cause the MEMS resonator beams 112 and 114 to oscillate in a tuning fork fashion, as indicated by arrows 122 and 124 , respectively. In response to the motion of the MEMS resonator beams 112 and 114 , the average capacitance between a sense electrode (not shown) and the MEMS resonator beams 112 and 114 changes at a substantially constant frequency at a constant temperature. The capacitance can be measured, and the resulting signal can then be used to generate a timing signal.
As also shown, the MEMS resonator 100 includes slots 130 positioned in different locations within the MEMS resonator beams 112 and 114 and the base 118 . The slots 130 are filled with a compensating material (e.g., oxide) that has a TCE with an opposite sign relative to the MEMS resonator material. As previously described herein, at higher temperatures, oxide typically becomes stiffer, while the MEMS resonator material (e.g., silicon) typically becomes less stiff. Thus, filling the slots 130 with oxide counters the changing properties of the MEMS resonator material over temperature. More specifically, the overall TCF of the MEMS resonator 100 is proportional to a weighted average of the TCE of the MEMS resonator material and the TCE of the oxide, based on the placement of the oxide in the strain field of the MEMS resonator 100 .
Placing oxide in slots within the MEMS resonator itself offers several advantages over growing oxide on the outside surfaces of the MEMS resonator, as is done in prior art approaches. One advantage is increased control over the oxide growth process. Oxide growth in the slots may be self-limiting because the amount of oxide cannot exceed the size of the slots. Another advantage is that if oxide is also desired on the outside surfaces of the MEMS resonator adding oxide within the slots allows the amount of oxide on the outside surfaces of the MEMS resonator to be reduced. A thinner oxide layer on the outside surfaces enables oxide to be grown in a larger number of MEMS resonator systems without conflicting with the geometric and spatial constraints of those systems. In addition, better frequency control of the MEMS resonator may be achieved because the characteristics of the MEMS resonator elements become more predictable with thinner layers of oxide on the outside surfaces of the resonator elements. Furthermore, reducing the thickness of the oxide layers grown on the MEMS resonator decreases the stresses within the MEMS resonator material resulting from a lattice mismatch between the oxide and the MEMS resonator material, thereby reducing the risk of stress-induced cracking. Finally, reducing the amount of oxide may result in improved transduction within the MEMS resonator.
Persons skilled in the art will recognize that oxide may be placed in/on the MEMS resonator using growth, deposition, or a combination of both growth and deposition. Therefore, one should understand that anywhere an oxide growth is discussed in the present application, oxide deposition or a combination thereof could be used as well.
Furthermore, in lieu of filling the slots with oxide, the slots described in the present application may be filled with any suitable compensating material that has a TCE with an opposite sign to the TCE of the MEMS resonator material. For example, in one embodiment, a MEMS resonator may be formed from silicon oxide (SiO 2 ), slots may be filled with Si, sacrificial material may be Si, and cap/liner material may be silicon nitride (SiN).
FIG. 1B illustrates a cross-section of the MEMS resonator beam 112 along line 140 of FIG. 1A . The cross-sectional view further illustrates the arrangement of the slots 130 within the MEMS resonator 100 , according to one embodiment of the present invention. As shown, H indicates the height of the MEMS resonator beam 112 , and W indicates the width of the MEMS resonator beam 112 . The slots 130 may be lithographically defined from the top face 144 , in the pattern illustrated in FIG. 1A , and extended all the way to the bottom face 142 , as illustrated in FIG. 1B , in the form of narrow trenches. The oxide can be introduced within the slots 130 through the processes of growth, deposition, or a combination thereof. The pattern and number of slots may also be varied to meet design goals.
Referring back now to FIG. 1A , when oscillating, as indicated by the arrows 122 and 124 , the MEMS resonator beams 112 and 114 are the resonating elements of the MEMS resonator 100 , and are subject to flexural stresses. Along the length L of the MEMS resonator beam 112 , the flexural stress is larger on outside sidewalls 141 and 143 and decreases towards the center of the MEMS resonator beam 112 . Similarly, along the length L of the MEMS resonator beam 114 , the flexural stress is larger on outside sidewalls 145 and 147 and decreases towards the center of the MEMS resonator beam 114 . In addition, for both the MEMS resonator beams 112 and 114 , the flexural stresses are relatively large near the base 118 and decrease towards the opposite end of each beam, away from the base 118 . Thus, areas 161 , 163 , 165 , and 167 near the base 118 indicate the regions of the MEMS resonator beams 112 and 114 that are subject to the largest flexural stresses. As described in greater detail in FIG. 2 , the greater the flexural stresses in a given area, the greater the dependence of the overall TCF of a MEMS resonator on the individual TCEs of the materials comprising that area. Therefore, placing the slots filled with oxide in the areas that experience large flexural stresses increases the effective contribution of the TCE of the oxide to the overall TCF of the MEMS resonator, which facilitates lowering the overall TCF of the MEMS resonator.
FIG. 2 is a conceptual diagram of a MEMS resonator 200 , according to another embodiment of the present invention. Similar to the MEMS resonator 100 , the MEMS resonator 200 includes MEMS resonator beams 212 and 214 , slots 230 filled with a compensating material (e.g., oxide) that has a TCE with an opposite sign relative to the MEMS resonator material, and a MEMS resonator anchor 216 that fixes a base 218 of the MEMS resonator 200 to an underlying handle wafer (not shown). Again, the MEMS resonator beams 212 and 214 of length L are mechanically coupled and oscillate in a tuning fork fashion, as indicated by arrows 222 and 224 , respectively, leading to the generation of a reference signal.
As shown, the MEMS resonator 200 differs from the MEMS resonator 100 in that outside sidewalls 241 , 243 , 245 , and 247 of the MEMS resonator beams 212 and 214 have serrated surface with a plurality of teeth. Cutting serrations into the outside edge of the resonator can shift the maximum strain field inward, along the base of the serrations near lines 251 , 253 , 255 , and 257 . For example, for the MEMS resonator beam 212 , the flexural stresses are largest along the lines 251 and 253 that extend along the base of the teeth and decreases towards the outside sidewalls 241 and 243 and towards the center of the MEMS resonator beam 212 . Similarly, for the MEMS resonator beam 214 , the flexural stresses are largest along the lines 255 and 257 that extend along the base of the teeth and decreases towards the outside sidewalls 245 and 247 and towards the center of the MEMS resonator beam 214 . Furthermore, for both the MEMS resonator beams 212 and 214 , the flexural stress is relatively large near the base 218 , and decreases to the tip of each beam. Thus, areas 261 , 263 , 265 , and 267 near the base 218 indicate the regions of the MEMS resonator beams 212 and 214 that are subject to the largest flexural stress, while the serrated teeth of the outside sidewalls 241 , 243 , 245 , and 247 experience minimal stress when the MEMS resonator beams 212 and 214 oscillate during operation.
In various embodiments, the serrations may be of any suitable profile. Therefore, one should understand that anywhere serrated teeth are discussed in the present application, other irregular profiles could be used as well. For example, instead of having the serrated teeth on the outside sidewalls, the MEMS resonator beams may include outside sidewalls with rounded teeth profile, a sinusoidal profile, an “arc-to-point” profile, a “skewed teeth” profile, an interlocked profile, or a combination thereof.
Enhancing the stiffness of the MEMS resonator beams 212 and 214 in regions that experience large stresses has a greater marginal impact on the overall stiffness of the MEMS resonator 200 than enhancing the stiffness in regions that experience lesser stresses. Thus, whenever possible, by placing slots filled with a compensating material in the regions of the largest stress, as shown with the slots 230 within the areas 261 , 263 , 265 , and 267 , the contribution of the compensating material in the slots 230 to the overall stiffness of the MEMS resonator 200 is increased. Whenever placing slots filled with the compensating material in the regions of the largest stress is not technically feasible, placing slots filled with the compensating material in the regions subject to larger stresses relative to other regions, the contribution of the compensating material in the slots to the overall stiffness of the MEMS resonator is still increased. Consequently, the contribution of the TCE of the compensating material to the overall TCF of the MEMS resonator, proportional to a weighted average of the TCE of the MEMS resonator material and the TCE of the compensating material, is also increased. As a result, the total amount of compensating material necessary to counteract the behavior of the MEMS resonator material and achieve a particular desired overall TCF value may further be reduced relative to prior art techniques. All of the advantages of further reducing the thickness of compensating material layers (e.g., oxide layers), discussed above, apply with equal force to the MEMS resonator 200 .
In addition, since serrating the outside sidewalls 241 , 243 , 245 , and 247 effectively shifts the regions of the largest flexural stresses within the MEMS resonator beams 212 and 214 further inward, the overall TCF of the MEMS resonator 200 is less sensitive to variations in the thickness of oxide grown on the outside sidewalls 241 , 243 , 245 , and 245 . Therefore, serrating the outside sidewalls 241 , 243 , 245 , and 245 provides the benefit of increased tolerance in oxide growth variations during fabrication of the MEMS resonator 200 .
FIGS. 3A through 3D illustrate the process of filling the slots 230 within the MEMS resonator 200 with oxide, according to one embodiment of the present invention. While the process is described with relation to the MEMS resonator 200 , the same process applies to filling with oxide the slots 130 within the MEMS resonator 100 .
FIG. 3A illustrates a cross-sectional view of the slot 230 etched in the MEMS resonator beam 212 before the oxidation process starts. The original boundaries of the bottom and top faces of the MEMS resonator beam 212 are shown as top face 342 and bottom face 344 , respectively. The original boundaries of the surfaces created by etching the slot 230 are shown as a left slot sidewall 313 and a right slot sidewall 315 . FIG. 3B illustrates the slot 230 after the oxidation process has started. The oxide grows substantially equally on the top face 342 , the bottom face 344 , the left slot sidewall 313 , and the right slot sidewall 315 , as indicated with the cross-hatched areas. As a result of oxide growth, the boundaries of the top and bottom faces 342 , 344 expand, as shown with oxide boundaries 352 and 354 . Similarly, the boundaries of the left and right slot sidewalls 313 , 315 expand as well, as shown with oxide boundaries 323 and 325 . During the oxidation process, the oxide may grow both outward the original boundaries (about 60% of the growth) and inward the original boundaries of the material (about 40% of the growth). Thus, the boundaries of the MEMS resonator material shift inwards, as shown with oxide boundaries 333 and 335 .
As the oxide continues to grow, the oxide boundaries 352 , 354 , 323 , 325 , 333 , and 335 expand further in their respective directions. Eventually, the lines 323 and 325 come so closer together that the slot 230 is plugged shut, as shown in FIG. 3C , leaving a small gap 330 . Since free oxygen molecules cannot easily reach the gap 330 , the oxide growth in the slot 230 stops. The moment in the oxidation process when the slot 230 is plugged shut is referred to herein as “pinch-off.” After pinch-off, the oxide continues to grow only on the top and bottom faces 342 , 344 , as illustrated in FIG. 3D , where the oxide boundaries 352 and 354 are expanded even further.
In different implementations, the slots 230 may be filled completely, by allowing the oxidation or deposition process to continue past pinch-off (as illustrated in FIG. 3D ), or partially, by stopping the oxidation or deposition process before pinch-off (as illustrated in FIG. 3B ). Completely filling the slot 230 with oxide increases the range of allowable oxide thickness and is attractive for manufacturing control because of the pinch-off. However, when the oxide boundaries 323 and 325 come into contact with each other, excessive in-plane stress and stress gradients may arise, which may be detrimental to the characteristics of the MEMS resonator 200 . For this reason, partial filling of the slots 230 may be preferred since the oxide boundaries 323 and 325 do not come into contact with one another. After the slots 230 are partially filled with oxide, the remaining gap in the slot 230 may be filled with a low-stress cap layer, such as silicon.
FIG. 4A illustrates the effects of placing slots filled with oxide in areas of high strain concentration on the TCF of a MEMS resonator, according to one embodiment of the present invention. As shown, a line 402 is a reference line, indicating a TCF of 0 ppm/° C. A line 404 represents the TCF of a conventional single ended cantilever beam MEMS resonator with a serrated 4 μm-wide beam for different oxide thicknesses on the outside sidewalls of the MEMS resonator beam. A line 406 represents the TCF of a conventional single ended cantilever beam MEMS resonator with a serrated 8 μm-wide beam for different oxide thicknesses on the outside sidewalls of the MEMS resonator beam. The term “conventional” implies that the MEMS resonator is uniformly oxidized on the surface and does not include slots with oxide within the MEMS resonator beam. When the conventional MEMS resonators do not contain any oxide on their surfaces (point 412 in FIG. 4A ), the TCF of those resonators is −30 ppm/° C. As shown, the slope of the line 406 is smaller than the slope of the line 404 , indicating that more oxide must be grown on the surface of the MEMS resonator with a 8 μm-wide beam compared to the MEMS resonator with a 4 μm-wide beam to reduce the TCF to a particular target value.
As also shown in FIG. 4A , line 408 represents the TCF of a single ended cantilever beam MEMS resonator with a serrated 19 μm-wide beam containing slots filled with oxide for different oxide thicknesses on the top and bottom faces of the MEMS resonator beam. Referring back now to FIGS. 3A through 3D , the point 412 on the line 408 corresponds to FIG. 3A , where the process to fill the slots with oxide has not yet started. Point 414 on the line 408 corresponds to FIG. 3B , where the slots are partially filled with the oxide. Point 416 on the line 408 corresponds to FIG. 3C , where, at pinch-off, the oxide plugs the slot shut. Between the points 412 and 416 , the slope of the line 408 is greater than the slope of the line 406 . Again, a greater slope indicates that a thinner layer of oxide is needed on the surface of the MEMS resonator with slots and a 19 μm-wide beam compared to the conventional MEMS resonator with a 8 μm-wide beam to reduce the TCF to a particular target value. The line 408 has a greater slope between the points 412 and 416 than the line 406 because, between the points 412 and 416 , the overall TCF of the MEMS resonator with slots is dominated by the oxide growth in the slots. As previously described, positioning the slots in the regions of the MEMS resonator beam that are subject to the largest flexural stresses increases the contribution of the oxide in the slots to the overall TCF of the MEMS resonator. As a result, the total amount of oxide on the surfaces of the MEMS resonator beam needed to decrease the magnitude of TCF of the MEMS resonator from −30 ppm/° C. to a particular target value is reduced. For example, as indicated with a line 430 , in order to reduce the TCF to −5 ppm/° C., 0.6 μm of oxide is required to be grown on the surfaces of the conventional MEMS resonator with a 8 μm-wide beam. However, only about 0.33 μm of oxide is required to be grown on the surfaces of the MEMS resonator with slots and a 19 μm-wide beam to achieve the same TCF.
Point 416 on the line 408 corresponds to FIG. 3D , where, after pinch-off, the oxide continues to grow on the bottom and top faces of the MEMS resonator beam. After the point 416 , the slope of the line 408 is less than the slope of the line 406 . The slope of the line 408 decreases after the point 418 because, after the oxide plugs the slots shut, the overall TCF of the MEMS resonator with slots is dominated by the oxide growth on the bottom and top faces of the MEMS resonator beam. As a result, after the point 416 , the overall TCF of the MEMS resonator with slots is not determined by oxide growth (deposition) on its sidewalls 241 , 243 , 245 , 247 because the serration of the surface routes the strain field away from oxide grown or deposited on these surfaces. On a MEMS resonator with slots but without the serration, the slope of the line 408 after the point 416 would be greater.
Persons skilled in the art will recognize that, in order to improve manufacturability, the slope of the TCF curve for a MEMS resonator, as the curve crosses through TCF=0, should be minimized. By doing so, the TCF of the MEMS resonator may remain within a desired range for a larger range of oxide thicknesses. For example, FIG. 4B is a magnified view of an area 420 where the TCF of the MEMS resonator with slots is within 1 ppm/° C. As shown, the value of oxide thickness for which the TCF of the MEMS resonator with slots is 0 ppm/° C. is 0.5 μm and the range of the oxide thickness for which the TCF of the MEMS resonator with slots is within ±1 ppm/° C. is 0.1 urn. Thus, the design of the MEMS resonator with slots achieves the desired overall TCF value with a thinner layer of oxide, while allowing variations in oxide thickness to be as large as ±10%. In addition, it allows for increased tolerance range in dimensions of resonator prior to oxide growth or deposition.
FIG. 5 sets forth a flow diagram of method steps for filling slots within the MEMS resonator 200 with oxide, according to another embodiment of the present invention. Again, while the process is described with relation to the MEMS resonator 200 , the same process applies with equal force to filling the slots 130 within the MEMS resonator 100 with oxide.
The method begins in step 502 , where the slots 230 are lithographically defined and fabricated. In step 504 , the slots 230 are lined with a liner material such as silicon, resistant to the release etchant, commonly hydrofluoric (HF) acid. In step 506 , oxide is added to the slots 230 through oxide growth, deposition, or a combination thereof. Depending on the particular application, the slots 230 may be filled with oxide completely or partially, as described above. In step 508 , the excess oxide is removed from the MEMS resonator 200 so that the oxide remains only within the slots 230 . Finally, in step 510 , the slots 230 are capped with a capping material resistant to the release etchant. Again, silicon may be used as a capping material.
FIGS. 6A through 6E illustrate the process of completely filling the slots 230 within the MEMS resonator 200 with oxide, according to the method steps of FIG. 5 . FIG. 6A illustrates the slot 230 etched in the MEMS resonator beam 212 (step 502 ). As shown, the MEMS resonator beam 212 is fabricated on top of a buried oxide layer 610 , which is fabricated on top of a handle wafer 615 . FIG. 6B illustrates the slot 230 lined with a liner material 620 resistant to the release etch process (step 504 ). FIG. 6C illustrates the slot 230 filled completely with oxide 630 (step 506 ). FIG. 6D illustrates the excess oxide 630 removed from the surfaces of the MEMS resonator beam 212 such that the oxide 630 remains only within the slot 230 (step 508 ). FIG. 6E illustrates the slot 230 capped with a capping material 640 (step 510 ).
FIGS. 7A through 7E illustrate the process of partially filling the slots 230 within the MEMS resonator 200 with oxide, according to the method steps of FIG. 5 . FIG. 7A illustrates the slot 230 etched in the MEMS resonator beam 212 (step 502 ). As shown, the MEMS resonator beam 212 is fabricated on top of the buried oxide layer 610 , which is fabricated on top of the handle wafer 615 . FIG. 7B illustrates the slot 230 lined with the liner material 620 resistant to the release etch process (step 504 ). FIG. 7C illustrates slot 230 partially filled with the oxide 630 (step 506 ). FIG. 7D illustrates the excess oxide 630 removed from the surfaces of the MEMS resonator beam 212 such that the oxide 630 remains only within the partially filled slot 230 (step 508 ). Finally, FIG. 7E illustrates the partially filled slot 230 capped with the capping material 640 .
The particular process that may be implemented to fill the slots 230 with oxide depends on when the oxidation process takes place in relation to the HF vapor etching step during the fabrication of the MEMS resonator 200 . Persons skilled in the art will recognize that the step of HF vapor etching is intended to etch the buried oxide layer 610 and release the MEMS resonator 200 . If the process of filling the slots 230 with oxide is carried out after the release etching step, then the process described in FIGS. 3A through 3D , above, may be implemented. If, however, the process of filling the slots 230 with oxide is carried out before the HF vapor etching step, then the HF vapor may etch not only the buried oxide layer 610 , but also the oxide within the slots 230 . In some devices, some etching of the oxide within the slots may be acceptable and a liner and cap are not required. Additionally, if compensating material is not substantially affected by release etchant, a cap/liner may not be needed. The additional steps of lining and capping the slots 230 with silicon, as described in FIGS. 5, 6A through 6E , and 7 A through 7 E above, are included to prevent the HF vapor from etching the oxide in the slots 230 when the buried oxide layer 610 is etched. In this manner, when the MEMS resonator 200 is released after the buried oxide layer 610 is etched with the HF vapor, the oxide remains embedded within the slots 230 .
In addition to the foregoing, the capping material 640 ensures that the surface of the MEMS resonator 200 remains conductive which prevents charge from accumulating on the surface of the oxide 630 . As a result, the electrostatic problems previously described herein may be eliminated. The liner material may also be made conductive for similar reasons.
The foregoing description applies to MEMS resonators that are comprised of resonating elements that exhibit flexural (bending) mechanical modes of resonance. Some resonator devices may include resonating elements that exhibit extensional (stretching) modes of resonance. Extensional resonators may also be temperature compensated using structures that include slots filled with a compensating material. FIG. 8 is a conceptual diagram of an extensional resonator 800 , according to one embodiment of the present invention. The extensional resonator 800 includes an extensional resonator beam 812 configured as a straight bar and anchored near its center with an anchor 816 . In other embodiments, extensional mode resonators may include plates, rings, or other shapes and structures.
The extensional resonator beam 812 oscillates in a stretching fashion, as indicated by arrows 822 and 824 , leading to the generation of a reference signal. The extensional resonator 800 also includes slots 830 filled with a compensating material (e.g., oxide) that has a TCE with an opposite sign relative to the MEMS resonator material.
In an extensional mode resonator, strain fields may be more uniformly distributed through the thickness and width of the resonator. For example, for the extensional resonator 800 , the lowest order extensional resonant mode will have its highest strain field in an area 865 (i.e., the area 865 is a region subject to the largest extensional stress). The maximum stress regions in an extensional mode resonator may not be situated near the edges of the resonator beam.
Similarly to the MEMS resonator 200 , enhancing the stiffness of the MEMS resonator beam 812 in regions that experience large stresses has a greater marginal impact on the overall stiffness of the MEMS resonator 800 than enhancing the stiffness in regions that experience lesser stresses. Thus, whenever possible, by placing slots filled with a compensating material in the regions of the largest extensional stress, as shown with the slots 830 within the area 865 , the contribution of the compensating material in the slots 830 to the overall stiffness of the MEMS resonator 800 is increased. Whenever placing slots filled with compensating material in the regions of the largest extensional stress is not technically feasible, placing slots filled with compensating material in the regions of larger stress rather than placing the slots with compensating material in the regions of lesser stress, the contribution of the compensating material in the slots to the overall stiffness of the MEMS resonator is still increased. Consequently, the contribution of the TCE of the compensating material to the overall TCF of the MEMS resonator, proportional to a weighted average of the TCE of the MEMS resonator material and the TCE of the compensating material, is also increased.
More specifically, for extensional mode resonating elements, experimentation has shown that a ratio of about 40% compensating material (e.g., oxide) to MEMS resonator material (e.g., silicon) effectively balances the TCF of the MEMS resonator. The ratio applies to the thickness of the MEMS resonating element in a plane perpendicular to the stretching movement of the MEMS resonating element.
FIG. 9 is a conceptual diagram of an electronic device 900 configured to implement one or more aspects of the present invention. As shown, electronic device 900 includes, without limitation, a timing signal generator 920 configured to provide a timing signal to application circuitry 910 . The timing signal generator 920 includes a MEMS oscillator sustaining circuit 930 . In one embodiment, the MEMS oscillator sustaining circuit 930 includes the MEMS resonator 200 , where the serrated MEMS resonator beams 212 and 214 are fabricated as shown in FIG. 2 . In another embodiment, the MEMS oscillator sustaining circuit 930 may include the MEMS resonator 100 , where the MEMS resonator beams 112 and 114 are fabricated as shown in FIG. 1 . In yet another embodiment, the MEMS oscillator sustaining circuit 930 may include the extensional resonator 800 , where the extensional resonator beam 812 is fabricated as shown in FIG. 8 , or any other suitable MEMS resonator according to the present invention. Furthermore, the MEMS oscillator sustaining circuit 930 includes a drive circuit (not shown) that drives the MEMS resonator 200 . Electronic device 900 may be any type of electronic device that includes application circuitry requiring a timing signal. Some examples of electronic device 900 include, without limitation, an electronic wrist watch, a personal digital assistant, or a cellular phone.
Using FIG. 9 as an example, in alternate embodiments, the MEMS resonator 200 may be disposed on/in the same substrate or on/in different substrates than the drive circuit. Moreover, the application circuitry 910 may be disposed on/in the same substrates as the MEMS resonator 200 and/or the drive circuit. FIGS. 10A through 10E illustrate different ways to position the MEMS resonator 200 , a drive circuit 1090 , and the application circuitry 910 on one or more substrates. In particular, the MEMS resonator 200 and/or the drive circuit 1090 and/or the application circuitry 910 may be integrated on/in the same substrate 1000 , as shown on FIG. 10A , on/in different substrates 1000 a , 1000 b and 1000 c , as shown on FIG. 10B , or on/in different substrates 1000 d , 1000 e , 1000 f , 1000 g , 1000 h and 1000 i , as shown on FIGS. 10C, 10D, and 10E . All permutations and combinations thereof are intended to fall within the scope of the present invention.
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. | A resonant member of a MEMS resonator oscillates in a mechanical resonance mode that produces non-uniform regional stresses such that a first level of mechanical stress in a first region of the resonant member is higher than a second level of mechanical stress in a second region of the resonant member. A plurality of openings within a surface of the resonant member are disposed more densely within the first region than the second region and at least partly filled with a compensating material that reduces temperature dependence of the resonant frequency corresponding to the mechanical resonance mode. | 7 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation-in-part of U.S. Ser. No. 08/817,391, filed Apr. 25, 1997 and a continuation-in-part of U.S. Ser. No. 09/986,414, filed Nov. 8, 2001, the entire disclosures of which are hereby incorporated by reference.
BACKGROUND OF INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to a process for the production of a floor strip such as a dilatation profile, a transition profile or a finishing profile. The present invention also relates to the features of the floor strip.
[0004] 2. Description of the Related Art
[0005] It is previously known to produce floor strips such as metal strips, wood veneer coated strips and strips of homogeneous wood. However, such floor strips generally do not adequately match the pattern of the other portions of the floor. Thus, there is a strong desire to bring about a floor strip with the same pattern as on a floor of thermosetting laminate. During the last few years these floors have become very usual. For instance they are made with a wood pattern, marble pattern and fancy pattern. Possibly you can use a homogeneous wood strip or a wood veneer-coated strip for a few of the wood patterned floors. Previously known strips do not go well together with all the other floor patterns.
[0006] These floor strips are provided in a floor system in order to provide a transition or edge to the floor, such as at the corner of the wall or between rooms. They may also be provided between rooms having different types of flooring, such as carpet and tile, or different heights or textures of tiles. However, conventional floor strips do not adequately provide a transition between differing floor types because they cannot adequately cover the gap between the differing floor coverings or the differing heights of the tiles.
[0007] However, it also a problem for sellers of floor strips to inventory differing types of transition profiles, especially in a pattern or color to match a single floor. Thus, there exists a need to provide a single floor strip which can satisfy a number of differing requirements, such a being useful as a finishing profile, a dilatation profile, and a transition profile.
SUMMARY OF INVENTION
[0008] The purpose of the present invention is to provide a floor strip with improved abrasion resistance and features to overcome the problems in the art.
[0009] According to the present invention it has quite surprisingly been possible to meet the above needs and bring about a process for the production of floor strips such as a dilatation profile, a transition profile or a finishing profile. The process comprises glueing, preferably under heat and pressure a thin decorative thermosetting laminate of post-forming quality having an abrasion resistance measured as IP-value>3000 revolutions, preferably >6000 revolutions, on a longitudinal carrier, which carrier preferably consists of a fibre board or a particle board with a rectangular cross-section and at least two opposite rounded-off edges.
[0010] The post-forming laminate is glued in one piece on the upper side and two long sides of the carrier via the rounded-off edges, whereupon one or more floor profiles having the same or different cross-section is machined from the laminate coated carrier. According to another embodiment the carrier can be provided with a rectangular cross-section with three rounded-off edges.
[0011] From the same body, the laminate clad carrier, several profiles with varying shape can be machined. Usually a milling machine is used for machining the different kinds of profiles from the laminate coated carrier. The carrier may also be molded to achieve various profiles which may be required. Additionally, the carrier is preferably water resistant or even waterproof. In a preferred embodiment the carrier consists of a high density fibre board made of fine fibres, such as known in the industry as medium density fiberboard (MDF) or high density fiberboard (HDF).
[0012] Advantageously, a heat and moisture resistant glue is used at the glueing. Preferably the glueing is carried out under heat and pressure. For instance, the pressure can be regulated by means of rollers which press the laminate against the carrier. The temperature can, for instance, be regulated with heating nozzles which can give an even current of warm air.
[0013] Suitably the post-forming laminate consists of at least one monochromatic or patterned paper sheet impregnated with a thermosetting resin, preferably melamine-formaldehyde resin and preferably one or more sheets for instance of parchment, vulcanized fibres or glass fibres. The last mentioned sheets are preferably not impregnated with any thermosetting resin, but the thermosetting resin from the sheets situated above will enter these sheets at the laminating step, where all sheets are bonded together. Alternatively, the sheet can be a metallic foil or a layer of paint.
[0014] Generally the term post-forming laminate means a laminate which is so flexible that it can be formed at least to a certain extent after the production thereof. Ordinary qualities of thermosetting decorative laminates are rather brittle and cannot be regarded as post-forming laminates.
[0015] Usually the post-forming laminate includes at least one uppermost transparent paper sheet made of α-cellulose and impregnated with a thermosetting resin, preferably melamine-formaldehyde resin. This so-called overlay is intended to protect an underlying decor sheet from abrasion.
[0016] Often at least one of the paper sheets of the postforming laminate impregnated with thermosetting resin, preferably the uppermost one, is coated with hard particles, e.g., those having a Moh's hardness of at least 6, preferably between 6 and 10, similar to the Moh's hardness of at least silica, aluminium oxide, diamond and/or silicon carbide. The hard particles have an average particle size of about 1-80 μm, preferably about 5-60 μm evenly distributed over the surface of the paper sheet. In a preferred embodiment the hard particles are applied on the resin impregnated paper surface before the resin has been dried. The hard particles improve the abrasion resistance of the laminate. Hard particles are used in the same way at the production of laminates which are subject to a hard wear such as flooring laminates.
[0017] The abrasion resistance of the post-forming laminates is tested according to the European standard EN 438-2.6: 1991. According to this standard the abrasion of the decor sheet of the finished laminate to the so-called IP-point (initial point) is measured, where the starting abrasion takes place. The IP-value suitably lies within the interval 3000-20000, preferably 3000-10000 revolutions. Thus, the manufacturing process according to the invention makes it possible to produce laminate clad profiles with the same surface pattern and about the same abrasion resistance as the laminate floorings they are intended to be used together with.
[0018] The carriers for the floor strips to which the post-forming laminate is glued can be made of differing profiles to accommodate the specific circumstance, namely whether a dilatation, transition or finishing profile is required. The profile, for example a dilatation profile, comprises a general T-shape whereby a first plane extending vertically along the length of the floor strip intersects about in the middle of a second horizontally oriented plane. A profile removes about half of the second plane to form a rotated upside down L-shape, which is used adjacent a wall or on a stepped surface. A dilatation profile is similar to a finishing profile, but the second plane is oriented off of horizontal or it is divided into two planes, one at a different level than the other, or one side is removed altogether, which provides a smoother transition between uneven tiles, a carpet and tile, or differing tile textures. The pattern of the profiles can also be adapted to other flooring materials than laminate floorings, such as parquette floorings and soft plastic floorings.
[0019] In order to overcome the problems associated with transitioning between carpet and tile, differing textures of tiles or differing heights of tiles, the second plane may have a tab portion on its tile/carpet engaging surface depending orthogonally away from the second plane and displaced away from the first plane. The tab is used to engage a reducer that extends between the floor surface and the engagement surface of the second plane. The reducer is configured to maintain a horizontal orientation of the second plane and provide a smoother transition between the tile surfaces in the finishing, transition or dilatation profile when they are used between uneven tile surfaces, differing tile textures or between carpet and tile. The tab portion fits into a groove on the upper surface of the reducer in mating fashion to create a solid lock between them.
[0020] Alternatively, the tab portion may be engaged into the edge of a tile panel on the floor. In this situation, the tiles adjacent to the transition area may require a groove cut into them near the transition. Such allows the tab portion to maintain a firm and locked relationship with the tile surface and provide a better transition between the tile surface and the respective profile. Further, a tab portion may be provided on both sides of the second plane respective to the first plane to further smooth the transition area between the first tile surface, the floor strip and the second surface.
[0021] The design of the tab may come in varying styles, there may be a straight block type tab, a t-nut type, various interlocking styles and a channel type arrangement. Such types depend on the particular requirements of the tiling circumstance.
[0022] This inventive floor strip according to the above may be used as a transition piece between various tongue and groove panels to provide a smooth and aesthetic transition between floor sections having dissimilar surfaces, such as those between a carpeted area and a tiled area, a thin tile area and a hardwood floor, two tile areas having differing textures, etc.
BRIEF DESCRIPTION OF THE DRAWINGS
[0023] The present invention will be explained further in connection with the embodiment example below and the enclosed figures of which:
[0024] FIG. 1 illustrates a post-forming laminate glued to a longitudinal carrier,
[0025] FIG. 2 illustrates a dilatation profile with a post-forming laminate glued thereto.
[0026] FIG. 3 illustrates a finishing profile with a post-forming laminate glued thereto.
[0027] FIG. 4 illustrates a transition profile with a post-forming laminate glued thereto.
[0028] FIG. 5 illustrates an exploded view of a dilatation profile extending between uneven tile surfaces.
[0029] FIGS. 6A-6C illustrate an assembled view of a locking tab/reducer assembly.
[0030] FIGS. 7A-7C illustrate an assembled view of a non-locking tab/reducer assembly.
[0031] FIG. 8 illustrates an assembled view of a dilatation profile having two tab portions locking with edge panels.
[0032] FIG. 9 shows a perspective view of the invention according to one embodiment of the invention.
[0033] FIGS. 10-14 illustrate tab designs according to other embodiments of the invention.
DETAILED DESCRIPTION OF THE INVENTION
[0034] In the figures of illustrating a floor strip 100 , the thickness of the post-forming laminate 1 has been magnified as compared to the size of the carrier 2 and the profiles, e.g. 3 - 5 respectively, to better illustrate that a post-forming laminate 1 is glued to the carrier 2 and the profiles 3 - 5 respectively. Of course the FIGS. 1-4 only show one embodiment of the carrier 2 and the profiles 3 - 5 respectively which can be produced according to the invention. Various other designs are possible as shown in the other drawing figures.
[0035] For example in one embodiment, a roll of transparent so-called overlay paper of α-cellulose with a surface weight of 25 g/m 2 is impregnated with an aqueous solution of melamine-formaldehyde resin to a resin content of 70 percent by weight calculated on dry impregnated paper. Immediately after the impregnation, aluminium oxide particles with an average particle size of 50 μm are applied to the upper side of the paper in an amount of 7 g/m 2 by means of a doctor-roll placed above the paper web. Thus, the hard aluminium oxide particles are then applied to the still-wet melamine-formaldehyde resin which has not dried.
[0036] The impregnated paper web is then fed continuously into a heating oven, where the solvent in the resin evaporates. Simultaneously, the resin is partially cured to so-called B-stage. Thereby the aluminium oxide particles are enclosed in the resin layer and accordingly concentrated to the surface of the product obtained which is usually called a prepreg. The prepreg web obtained is then rolled again.
[0037] A roll of conventional non-transparent decor paper with a decor pattern printed thereon and having a surface weight of 80 g/m 2 is treated in the same way as the overlay paper except for the fact that no aluminium oxide particles are applied and that the resin content was 50 percent by weight calculated on dry impregnated paper.
[0038] A roll of unimpregnated parchment with a surface weight of 120 g/m 2 is used at the production of the post-forming laminate.
[0039] The two prepreg webs impregnated with melamine-formaldehyde resin and the unimpregnated parchment web are then pressed between two press bands of a continuous laminating press to a decorative post-forming laminate. At the pressing, a prepreg web of α-cellulose is placed on top with the side with the hard particles directed upwards. Underneath follows a prepreg web of decor paper and at the bottom a web of parchment. The prepreg webs and the parchment web are pressed together at a pressure of 35 kp/cm 2 and at a temperature of 170° C. The decorative post-forming laminate obtained is then cut with roller knives to strips of suitable length and width.
[0040] A longitudinal carrier 2 with a rectangular cross-section and two opposite rounded-off edges according to FIG. 1 are machined from a fibre board or other substrate material by means of a milling machine. The fibre board is a water resistant board of so-called MDF-quality (medium density fibre board quality) or, alternatively, HDF quality (high density fibre board quality), made of finely divided fibres with an adhesive to bond the fibres together.
[0041] A strip of post-forming laminate 1 is now glued under heat and pressure to the longitudinal carrier 2 with a heat and moisture resistant glue. The pressure is regulated with rolls which press the laminate against the carrier and the temperature 1 is regulated with heating nozzles which blow an even current of warm air.
[0042] Following the above process, the abrasion resistance of the post-forming laminate obtained was measured. Then a value for the IP-point amounting to 7000 revolutions was obtained.
[0043] The different structures and designs of the profiles for floor strip 100 , namely the dilatation, finishing and transition will now be described with respect to FIGS. 2-9 . A dilation profile 3 according to FIG. 2 can be machined from the laminate clad carrier by milling. Two finishing profiles 4 according to FIG. 3 or one transition profile 5 according to FIG. 4 can be produced from the same carrier. This results in a rational and cost-saving production. Alternatively, the carriers can be the shape as shown in FIGS. 2-9 before the post-forming of the laminate is commenced.
[0044] FIG. 5 shows an exploded view of one of the preferred embodiments of the invention, wherein floor strip 100 is attached between two differing sets of tiles, thin tile 70 and thicker tongue and groove tiles 80 and 81 (shown in mating relationship), all on a subfloor 500 . FIG. 6A shows the components of FIG. 5 assembled together. In these figures, floor strip 100 is a dilatation profile having a T-shape, with a first plane 50 arranged vertically in use and a second plane 60 oriented horizontally and connecting to the first plane along its mid-section forming a “T.” The second plane overhangs the first plane on a first side 61 and a second side 62 . A tab 180 extends from the bottom plane of first side 61 of the second plane.
[0045] Due to the differing heights of the tiles 70 and 80 / 81 , a reducer 90 will be required to provide a smooth transition. Reducer 90 has a height corresponding to the height difference between the tiles and also has a groove 91 on its upper surface for acceptance, in a locking manner, of tab 180 . Upon assembly of tiles 70 , 80 and 81 and floor strip 100 , the tab fits into groove 91 and then the reducer is assembled in mating position between an edge 71 of tile 70 and the first side 61 of the second plane. The design of the tab and reducer prevents the reducer from laterally moving in relation to floor strip 100 in an assembled condition. Although a simple tongue and groove design is shown, other engagement means may be used (See FIGS. 9A-9F , discussed below) which have locking designs which lock the floor strip and reducer together. At each of these mating portions, glue may be used to additionally secure the components together. The reducers 90 (as well as the reducers of the subsequent described embodiments) may carry on an exposed outer surface a pot forming laminate (not shown) in a manner similar to that shown in FIGS. 1-4 .
[0046] Reducer 90 may have alternate designs, which are illustrated in FIGS. 6B and 6C . Reducer 90 , shown in FIGS. 5, 6A and 6 B, has a sloped portion 93 , which provides a more gradual transition between a tiled floor section having a higher height than an adjacent floor tile section. On the other hand, Reducer 95 , shown in FIG. 6C , has a vertical side 96 , which would provide more of a small step between the different tile floor sections.
[0047] Another embodiment of the invention is shown in FIGS. 7A-7C , whereby instead of tab 180 locking into a reducer, it provides a back stop for a reducer 97 which does not have any groove. Other aspects of this embodiment are congruent to those of the previous embodiment and will not be repeated herein.
[0048] Reducer 97 is more or less a rectangular box design having one sloped side 109 which as in the previous embodiment provides a gradual transition between floor heights. Reducer 97 does not have a groove, rather the back side 99 is abutted against tab 180 when floor strip 100 and reducer 97 are in their assembled positions, as shown in FIG. 7A . A glue or other adhesive may be used to maintain the parts in their positions and prevent reducer 97 from laterally moving in relation to floor strip 100 . Alternatively, reducer 98 may be used in place of reducer 97 . Reducer 98 has a rectangular box shape which provides a step between floor heights rather than in a sloped fashion.
[0049] A further embodiment of the invention is shown in FIG. 8 . In this embodiment, floor strip 100 is used between two adjacent floor tile sections having similar heights. Further, both first side 61 and second side 62 of the second plane 60 have tabs 180 and 181 , respectively. Tiles 200 and 210 have grooves 201 and 211 respectively. Tabs 180 and 181 fit into grooves 201 and 211 by a tongue and groove style, however, other engagement styles may be used (See FIGS. 9A-9F below) which either positively lock the parts together or simple provide a guide for assembly. Such a design does not require the use of a reducer between the tile and the floor strip.
[0050] The tab and reducer groove need not be a simple tongue and groove design, as outlined in FIGS. 5-8 . These were described merely by way of example using floor strip 100 with tab portion 180 as shown in FIG. 9 . Alternatives of the tab on the floor strip in conjunction with a reducer are shown in FIGS. 10-14 . Additionally, the reducers described in conjunction with the invention as a spacer between uneven floor tiles is not necessary. Should the tiles have similar height, a reducer may be removed and such slots which are described in the reducer may also be cut into the appropriate floor tile for positive locking or prevention of associated movement.
[0051] In FIG. 10A , a tab 1800 on floor strip 101 has the shape of a t-nut. An associated reducer 1000 has a shape similar to the t-nut cut through its longitudinal length thereof. Tab 1800 fits into the reducer 1000 by sliding the tab into an end portion of the reducer and along the length of the reducer. Such a design allows for a positive locking in a lateral direction while allowing movement along the longitudinal axis of the floor strip.
[0052] The designs of the tab portion as shown in FIGS. 11A, 12A and 14 A show a tab portion that snaps into the associated reducer. In FIG. 11A , a tab 1800 of floor strip 102 has a pair of upwardly facing angled teeth 1850 and 1851 . A reducer 1100 used in association with tab 1800 has a slot 1105 cut there through having an opening congruent to the design of the tab. When tab 1800 and reducer 1100 are assembled together, floor strip 102 is placed atop the reducer. Upon sufficient pressure on the floor strip, tabs 1801 will snap into the slot 1105 . Teeth 1850 and 1851 prevent tab 1801 from being removed from slot 1105 of reducer 1100 providing a positive locking together.
[0053] Tabs 1802 , 1820 and 1803 shown in FIGS. 12A and 14A , have a similar design for the upwardly facing teeth as shown in FIG. 11A , but have a differing number of teeth. Similarly, reducers 1200 and 1400 , used in association with these tabs respectively, also have slots 1205 and 1405 which are congruent to the associated tabs. A tile 1225 also has a slot near its edge for acceptance of the tab 1820 . Each slot design allows for the tab portion to be snapped into the associated slot for a positive locking between the tab and the slot. Although the slot drawn in these figures has a shape congruent to the shape of the associated tab, such is not required. The slot must only be of sufficient design whereby the tab can snap into the slot and whereby the design of the slot prevents removal of the tab. FIG. 12B also shows a floor strip 103 having a pair of tabs whereby the tabs snap into both a reducer and the associated tile. However, such a specific case is not required. Floor strip 103 may be snapped into a pair of tiles or a pair of reducers.
[0054] In FIG. 13A , a floor strip 104 has a pair of spaced tabs 1380 and 1381 having a generally triangular profile and extending along the length of the floor strip. Tabs 1380 and 1381 provide a channel by which reducer 1300 is held between the tabs under floor strip 104 . Such a design prevents lateral movement of reducer 1300 in relation to floor strip 104 .
[0055] Although the present invention has been described and illustrated in detail, such explanation is to be clearly understood that the same is by way of illustration and example only, and is not to be taken by way of limitation. Other modifications of the above examples may be made by those having ordinary skill which remain within the scope of the invention. For instance, the examples are described with reference to a dilatation profile for the carrier of the floor strip. However, such tab and reducer designs work just as well with a finishing profile as well as a transition profile, and whether used on carpet or floor tiles. | A thin decorative thermosetting laminate of postforming quality is glued to a longitudinal carrier to form a floor strip. The laminate has a thermosetting resin as well as hard particles impregnated therein to increase the abrasion resistance of the laminate. The carrier generally has a cross section of a dilatation, transition or a finishing profile, depending on the intended use of the floor strip. The floor strip has a tab portion on a surface that engages a channel on a floor tile or a reducer. The tab portion locks the floor strip into place and prevents movement of the floor tile or the reducer with respect to the floor strip. | 1 |
FIELD OF THE INVENTION
The present invention relates to a method and apparatus for introducing and removing through-the-flowline (TFL) tools from a subsea wellhead assembly. More particularly, the present invention relates to a method and apparatus for introducing and removing at least one TFL tool using a remotely installed lubricator adapted to transport TFL tools to and from the subsea wellhead assembly.
BACKGROUND OF THE INVENTION
In the production of subsea wells, such as oil and gas wells, it is a common practice to use a subsea wellhead assembly. When using such an assembly subsea oil well servicing and completion operations are often performed with TFL tools. TFL operations are preferred because the amount of support facilities necessary to conduct the operation is minimal. That is, an immediately adjacent platform or support structure is not necessary. However, TFL operations do require a particular configuration of seafloor equipment. The subsea wellhead must be designed to guide any TFL tool smoothly through the flowline or tubing into the well's tubing string. Furthermore, TFL operations usually require flowline communication between a surface location, such as an operating station, and the subsea wellhead assembly. Frequently, this connection is made with a dual completion flowline which provides a circulation path between the operating station and the well. Typical TFL operations using TFL tools include paraffin scraping, bottomhole pressure and temperature measurements, workover operations, and replacement of standing valves and sub-surface safety valves.
Notwithstanding the added advantages of TFL operations, the additional expense associated with the initial investment to provide TFL capability is high. This added expense is due primarily to increased costs for the dual flowline, the dual completion hardware, and operational costs related to drilling and completing the well for TFL operation. Additionally, a TFL wellhead is a relatively complex piece of equipment and generally requires special fabrication considerations.
Accordingly, the need exists for an improved method and apparatus which would permit the use of TFL tools and the performance of TFL operations without the added expense and hardware associated with providing dual completion lines and associated equipment.
SUMMARY OF THE INVENTION
The present invention is directed to a method and apparatus for introducing and removing at least one TFL tool using a remotely installed lubricator adapted to transport the TFL tool to and from the subsea wellhead assembly.
The apparatus includes a lubricator or a hollow elongate member which is adapted to support at least one TFL tool. One end of the elongate member is sealed while the other end is open or temporarily closed and, in any event, adapted to engage the receiving end of the subsea wellhead assembly. The apparatus includes an aligning mechanism to position the open end of the elongate member near the receiving end of the wellhead assembly. Means are provided for engaging the open end of the elongate member with the receiving end of the wellhead assembly. This engaging mechanism is capable of providing a pressure-tight seal. The apparatus also includes means for circulating fluid within the elongate member and the wellhead assembly once the elongate member and the wellhead assembly are engaged. Such a circulation permits the transfer of the TFL tool either from the elongate member to the wellhead assembly or from the wellhead assembly to the elongate member.
The method comprises the steps of lowering an elongate member which has been adapted to contain at least one TFL tool to the wellhead assembly, positioning the open end of the elongate member adjacent the receiving end of the wellhead, engaging the elongate member to the wellhead thereby providing fluid communication between the wellhead assembly and the interior of the elongate member, and circulating fluid within the member and the wellhead to transfer the TFL tool between the member and wellhead assembly.
Examples of the more important features of this invention have been summarized rather broadly in order that the detailed description which follows may be better understood. There are, of course, additional features of the invention which will be described hereinafter and which will also form the subject of the claims appended hereto.
BRIEF DESCRIPTION OF THE DRAWINGS
In order to more fully understand the drawings used and the detailed description of the present invention, a brief description of each figure is provided.
FIG. 1A is an elevation view of the apparatus of the present invention with a single elongate member.
FIG. 1B is a plan view of the apparatus shown in FIG. 1A.
FIG. 2 is an elevation view of the subsea wellhead assembly shown in a configuration adapted to receive the apparatus of the present invention.
FIG. 3 is a simplified illustration of the subsea wellhead assembly shown in FIG. 2.
FIG. 4A is an elevation view of the apparatus of the present invention with two elongate members.
FIG. 4B is a plan view of the apparatus shown in FIG. 4A.
FIG. 5 is an elevation view of the apparatus of the present invention being maneuvered by a remotely operated vehicle.
FIG. 6 is a simplified illustration showing the engagement of the apparatus with the subsea wellhead assembly.
FIG. 7 is an illustration of the circulation path established for the removal of a TFL tool, in this case a sub-surface safety valve located in the wellbore.
FIG. 8 is an illustration of the circulation path shown in an open mode ready to transfer a TFL pulling tool to the wellbore.
FIG. 9 is similar to FIG. 8 except that the pulling tool has engaged the sub-surface safety valve and is ready to transfer the valve from the wellbore to the apparatus.
DETAILED DESCRIPTION OF THE INVENTION
Referring now to FIGS. 1A-9, and with particular reference to FIGS. 1A-3, the apparatus "A" of the present invention is shown comprising an elongate member 10 attached to a clamping mechanism 12. The clamping mechanism 12 may be a clamp connector as generally described in John E. Ortloff's U.S. Pat. No. 4,225,160. However, it will be clear to those skilled in the art based on this disclosure that a bolted or hydraulically actuated clamping mechanism may be used, such as a bolted-flange connection. The elongate member 10 is shown sealed at one end 13 with a cap 14 but is open at the other end 16. The elongate member 10 and the clamping mechanism 12 are supported by a frame assembly 18. The apparatus includes docking prongs 20 which may be an integral part of the frame assembly 18 or, alternatively, attached to the frame assembly 18 for added rigidity.
The elongate member 10 is also known as a lubricator to those skilled in the art which is understood to mean that the inner diameter of the member 10 is generally larger than the inner diameter of the production tubing string 22 of the well 32 (see FIG. 3). This permits the easy manual installation of TFL tools at a support station, such as a surface vessel 19. Since TFL tools are advanced by pressurized fluid using tight-fitting locomotion pistons which require several hundred pounds of force, the manual installation of TFL tools by field personnel into a hollow member of the same diameter of the tubing string is difficult. Consequently, a larger diameter tube is used initially. The larger diameter is usually only 1/2" or so larger than the diameter of the production tubing string. But this is usually enough to permit easy installation and yet still provide enough seal around the pistons to advance the tool into the tubing string without problems. Lubricators are available commercially with single or dual elongate members, see for example Model No. FN1820 manufactured by Otis Engineering Corporation of Dallas, Tex. and shown at page 45 of Otis' 1981 Catalogue No. 5113B. Henceforth, however, the term "elongate member" shall be used instead of lubricator.
Referring back to FIG. 1A, an umbilical cord 24 extends from the support station 19, which would typically be a platform or a surface vessel, to the elongate member 10. The umbilical cord 24 as shown shrouds dual pressure conduits 26 and 28. The conduit 26 extends from the support station, through a valve 27 to the elongate member 10 and is in fluid communication with the interior of the elongate member 10 when valve 27 is open. The conduit 28 extends from the support station through a valve 29 which is closed at the time of installation and terminates proximate the clamping mechanism 12.
FIG. 1A is an elevation view of the apparatus of the present invention shown with a single elongate member 10. FIG. 1B is a plan view of the same apparatus shown in FIG. 1A. In FIGS. 1A and 1B the elongate member 10 is shown in a horizontal mode; however, it will be obvious to anyone skilled in the art based on this disclosure that for the performance of certain TFL operations, such as pigging operations, gravity assistance can be beneficial and in that event the elongate member may be positioned in a vertical mode.
Referring now to FIGS. 2 and 3, a subsea wellhead assembly 30 is shown which has been modified for use with the apparatus of the present invention. The wellhead assembly is occasionally referred to by those skilled in the art as a "christmas tree". The wellhead assembly is typically located above a well 32 from which oil and/or gas is to be produced. FIG. 3 is a simplified illustration of the subsea wellhead assembly shown in FIG. 2. The well 32 is shown with a TFL tool 34 located below the wellhead assembly 30 but within the tubing string 22. The tubing string 22 extends to the top of the christmas tree where a well cap or tree cap 36 is located. A production pipeline 38 extends from the tubing string 22 to shore or an offshore storage facility (not shown). The wellhead assembly 30 includes a receiving conduit 40 which is capable of providing open fluid communication with the well 32 when the valves 42 and 44 are open. The wellhead assembly 30 also includes docking receptacles 50 which are designed to mate with the docking prongs 20. Collectively, the receptacles 50 and the prongs 20 are referred to hereinafter as the docking hubs. Once fully engaged, the clamping mechanism 12 is in a proper position for sealably engaging the elongate member 10 with the receiving end 41. Hereafter, the clamping mechanism may be referred to as such a means for sealable engagement.
It may be preferable to use a looped receiving conduit 40A as shown in FIG. 2 as opposed to a 90° elbow conduit 40 as shown in FIG. 3. During TFL operations there is a possibility that a TFL tool may get stuck as it straddles valves 42 and 44. By using a looped receiving conduit 40A and placing the valve 42 near the docking receptacles 50, it is possible to get sufficient length of conduit 40A between valve 42 and valve 44 to locate an entire TFL tool without straddling both valves. The wellhead assembly also includes a conduit 52 in open communication at one end 54 with the interior of the well 52 and terminating at its other end 56 proximate the receiving end 41 of the conduit 40. The receiving end 41 as shown in FIG. 2 would usually include mating flange 43 which the clamping mechanism 12 would engage. For details of an example, please see John E. Ortloff's U.S. Pat. No. 4,225,160, which patent is hereby incorporated by reference. Referring back to FIG. 3, a valve 58 is located on pipeline 38 to close off the pipeline when a TFL tool is to be run as described below.
With reference to FIGS. 4A and 4B, an alternate embodiment of the apparatus of the present invention is shown. The principal modification of this embodiment is the provision of dual elongate members 110 and 111 which simplifies the operation of the present invention as will be apparent based on the following disclosure. This alternate embodiment also includes a diverter 60 which is used to alternate fluid communication between each elongate member 110 and 111 and the receiving end 41 of the receiving conduit 40. The diverter 60 as shown is well known to those skilled in the art, see for example B. Van Bilderbeck's U.S. Pat. No. 4,133,418 and Otis diverter Model No. FN1810 shown at page 45 of Otis' 1981 Catalogue No. 5113B. The alternate embodiment includes an umbilical cord 124, conduits 126 and 128, clamping mechanism 112, and docking prongs 120 identical to corresponding items described earlier with respect to the single elongate member embodiment.
With reference to FIG. 5, a remotely operated vehicle 62 is shown transporting the apparatus of the present invention from a support station to the subsea wellhead assembly. Such vehicles are commercially available, for example the "Gemini" model manufactured by Ametek Straza Corporation of San Diego, Calif. or the "Trident" model manufactured by Perry Offshore, Inc. of Riviera Beach, Fla. Alternatively, the apparatus may be lowered by a hard wireline 25 as shown in FIG. 6. In FIG. 6 the umbilical cord 24 described earlier with respect to FIGS. 1A and 1B and the wireline 25 are the same. Once the apparatus is properly aligned and docked via the docking hub, the clamping mechanism may be engaged.
Reference is now made to FIGS. 7 through 9 wherein the operation of the apparatus of the present invention and the wellhead assembly will be described. Collectively, the apparatus and the wellhead assembly will be referred to as the system. The operation of the present invention will be described with respect to the replacement of a sub-surface safety valve located in the wellbore, typically near the wellhead assembly. The use of such sub-surface safety valves is quite common. Their purpose is obvious based on the descriptive title. They are used to automatically seal off the well tubing in the event of an emergency. However, the use of the present invention is not limited to the replacement of sub-surface safety valves. It will be obvious to anyone skilled in the art based on this disclosure that the present invention may be used for the performance of any number of TFL operations such as the replacement of standing valves, the positioning of pressure and temperature survey tools, the installation of gas lift valves, etc.
Once the apparatus has engaged the wellhead assembly as shown and described above with respect to FIG. 6, the clamping mechanism 12 is actuated and establishes fluid communication between the elongate member 10 and the interior of the conduit 40 and the well 32. It will be obvious to anyone skilled in the art based on this disclosure that the clamping mechanism will be providing a pressure-tight or leak-proof connection between the elongate member 10 and the receiving end 41 of the conduit 40. Previous reference to John E. Ortloff's U.S. Pat. No. 4,225,160 as an example of a type of clamping mechanism provides for such. Furthermore, when such a connection is made, another simultaneous connection should be made connecting the end of conduit 28 with the end of conduit 52. Such a connection would be made probably in the flange area of the clamping mechanism. Techniques which could be used to effect such a pressure-tight connection between conduits 28 and 52 are well known to those skilled in the art.
Thus, a circulation path is established as shown in FIG. 7 which extends from the surface support vessel (19 in FIG. 1A) through the conduit 26 of umbilical cord 24, the elongate member 10, the conduit 40, the well 32, and conduits 52 and 28. This path is shown in FIG. 7 by the arrows 70. With reference to FIG. 8, the permit the introduction of a tool string (which includes locomotion pistons 74 and a pulling tool 72), valves 27, 29, 42 and 44 are opened and valve 58 is closed. Pressure is then introduced into conduit 26 at the surface via a pump 77 (see FIG. 1A) which permits the locomotion of the pulling tool 72 through the elongate member 10, the receiving conduit 40 and down to the TFL safety valve 34A. Such pulling tools 72 are well known to those skilled in the art such as Otis' type G pulling tool, Model MS-2034. Once the pulling tool 72 has arrived at the safety valve 34, it engages the top of the safety valve 34 for retrieval using state-of-art TFL equipment.
Referring to FIG. 9, circulation is then reversed. That is, pressure is introduced through conduit 28 as opposed to conduit 26. This establishes a pressure build-up below the locomotion pistons 74 which advances the tool string 74/72 upwardly. This results in the advancement of the tool string 74/72 with attached valve 34A into the elongate member 10. Valves 27, 29, 42 and 44 are then closed and the clamping mechanism 12 disengaged. The apparatus along with the tool string 74/72 and the old sub-surface safety valve 34A is then retrieved. At the surface a new sub-surface safety valve is installed in the elongate member 10 and the apparatus is returned to the wellhead assembly 30 and reconnected as described above. The new sub-surface safety valve is then installed within the well 32 in a manner similar to that described above with respect to the advancement of the tool string 74/72 into the well 32.
In the event the alternate embodiment as shown in FIGS. 4A and 4B is used, the tool spring 74/72 and retrieved safety valve 34A are returned to the first elongate member 110 in a manner similar to the single elongate member embodiment except that the apparatus is not disconnected. The diverter 60 is then activated which permits fluid communication between the second elongate member 111 and interior of the wellhead assembly 30 and the well 32. Circulation is established within the second elongate member, the wellhead, and the well tubing. A new sub-surface safety valve with a second tool string previously attached to it is then advanced through the diverter, the receiving conduit 40 and down to the location of the old sub-surface safety valve. At that time, the new sub-surface safety valve is disconnected and the tool string retrieved into the second elongate member. The valves 127, 129 and 42 are then closed and the clamping mechanism is disengaged. The apparatus is then retrieved.
The locomotion, connection, disconnection, and retrieval of TFL tools are well known to those skilled in the art and are described in detail in various oil industry equipment catalogues, such as Otis Engineering Corporation Bulletin No. 5113B, 1981 ed.
The operation of the valves 27 (127), 29 (129), 42, 44 and 58 during the performance of the TFL operation may be performed by a remotely operated vehicle well known to those skilled in the art. Alternatively, the valves may be operated hydraulically within a subsea production system as described in U.S. Pat. No. 3,777,812, or manually by a diver.
The present invention has been described in terms of various embodiments. Obviously, many modifications and alterations based on the above disclosure will be apparent to those skilled in the art. It is, therefore, intended to cover all such equivalent modifications and variations which fall within the scope of the claims appended hereto. | An apparatus and method is described for introducing and removing TFL tools from a subsea wellhead assembly. The apparatus includes an elongate member adapted to hold at least one TFL tool, docking hubs for aligning the elongate member with the wellhead, a clamping mechanism or the like for engaging the elongate member with the wellhead and a circulation for circulating fluid within the elongate member and the wellhead to transport the TFL tool between the elongate member and the wellhead. In another embodiment, the apparatus includes at least two elongate members and a diverter located between the elongate members and the clamping mechanism. The diverter permits alternate fluid communication between each elongate member and the wellhead assembly. The method comprises the steps of lowering the elongate member containing a TFL tool to the subsea wellhead assembly, positioning the elongate member adjacent the wellhead assembly, engaging the elongate member to the wellhead assembly, the then circulating fluid within the elongate member and the wellhead assembly to transport the TFL tool between the elongate member and the wellhead assembly. | 4 |
BACKGROUND OF THE INVENTION
(a) Field of the Invention
This invention relates to a protective device for use in connection with tools used for cleaning floors. More particularly, it relates to a shield or cover for wet mops that are commonly used for cleaning floors in commercial buildings, schools, and homes, and to the mop upon which the shield is mounted. The shield is mounted on the mop handle, and its position is adjustable up or down on the handle depending on whether or not the mop is in use.
In many commercial buildings, schools and the like that have hard surface floors such as concrete, stone, tile, vinyl or similar, the floors are conventionally cleaned with what is termed a wet mop. A wet mop comprises an elongated shaft or handle with a water absorbable mop head attached to the lower end of the handle. The water absorbable head generally comprises a plurality of cotton ropes of various dimensions tied together at the top, so as to form a single unit. The mop head can also be formed of water absorbable cloths, if desired.
In the mopping operation, water, which may or may not contain a detergent, is spread on the floor through various means, and the floor is swabbed with the mop. The mop head cleans the floor and absorbs the water which contains dissolved dirt and other contaminants. The dirty water is then wrung out of the mop head, and the process repeated until an entire floor is cleaned.
It is often desirable to use different mops for different sections of a building. That is, it is desirable to use one specific mop for bathrooms whose floors are frequently contaminated with urine, and another for less contaminated areas of a building such as hallways, etc. The mops are frequently carried from place to place, and so it is desirable to protect the clothes and skin of the person carrying the mop from coming into contact with, and being contaminated by the wet mop head. It is also desirable to be able to mark the mops in a manner that enables one to identify which mop is designed for specific areas.
This invention is concerned with a mop upon which is mounted a device for protection of a wet mop head, and for identification of mops designated for specific uses.
(b) Description of Related Art
U.S. Patent Publication No. 2006/0016031, Lianes, published Jan. 26, 2006, describes a cylinder attachment slideably mounted on a mop handle to wring water out of a mop. The cylinder has an array of apertures in its lower wider portion for release of the mop water when the dirty water-laden mop head is compressed inside it.
U.S. Pat. No. 3,846,862, Botting, issued Nov. 12, 1974, describes and claims a sheath for a curling broom designed to receive and to support the cornstalk brush of a curling broom to improve the effectiveness and life thereof. U.S. Pat. No. 1,476,396, Dickson, issued Dec. 4, 1923, describes and claims a sanitary broom mop. In this invention a broom is covered with a soft material that serves as a mop for wiping floors, walls, and the like.
U.S. Pat. No. 3,364,512, Yamashita, issued Jan. 23, 1968, describes and claims a mop squeezing cover which is slidable on the mop handle. When the squeezer is slid on the handle over the mop head, the squeezer wrings the water out of it, enabling the mop head to be reused. None of the above described patents disclose or make obvious the device of the present invention.
BRIEF SUMMARY OF THE INVENTION
The present invention is a mop upon which is mounted a protective mop shield or cover that is slideably mounted on the handle of the mop, and capable of being lowered over the head of the mop to protect it from damage, and to protect individuals who may be carrying the mop from coming into contact with a wet or contaminated mop head. The protective shield can also be marked, so as to enable a person to identify the purpose for which the mop is to be, or has been used.
BRIEF DESCRIPTION OF THE SEVERAL VIEWS OF THE DRAWINGS
FIG. 1 is a perspective view of the slider mechanism of the mop shield of the invention.
FIG. 2 is an exploded view of the slider mechanism for securing the mop shield to the handle of a mop.
FIG. 3 is a side view of the shield or cover portion of the mop shield of the invention.
FIG. 4 is an view of the slider mechanism of FIG. 2 to which is attached a shield or cover for the head of a mop.
FIG. 5 is a perspective view of the mop of the invention showing the mop shield in a raised position relative to the head of the mop.
FIG. 6 is a perspective view of the mop of the invention showing the mop shield in a lowered position with the cover portion enclosing the mop head.
FIG. 7 is a perspective view of the mop shield of the invention showing its position on a mop handle being adjusted by the user.
DETAILED DESCRIPTION OF THE INVENTION
The mop and mop shield of the invention is best described with reference to the figures. As shown in FIGS. 5 and 6 , the mop 10 of the invention comprises an elongated handle 12 with a mop head 14 attached at the lower end thereof. The handle 12 can be made of wood, plastic, metal, or any other suitable material. The head 14 is formed of a plurality of water absorbable ropes, preferably cotton, but it can be made of any water absorbable material. A mop shield 16 is attached to the handle of the mop 12 and is slideable relative thereto.
The shield 16 can be separated into two distinct components. The first component, as shown best in FIG. 1 , and the exploded view of FIG. 2 , comprises a slider unit or mechanism 18 that is slideable up and down the mop handle 12 . The slider mechanism 18 comprises an elongated tubular unit 20 whose internal diameter is slightly larger than the external diameter of the handle 12 of the mop 10 with which it is being used. In a preferred embodiment, the length of the tubular unit is 5¾ inches, its external diameter is 1 9/16 inches, and its internal diameter is 1⅜ inches. The tubular unit 20 has an upper end 22 and a lower end 24 . A pair of wings 26 , extend outwardly and substantially horizontally from the lower end 24 thereof. The tubular unit 20 has a threaded section 28 around its periphery above the wings 26 . In a preferred embodiment, the wings are 1⅞ inches in length, and ¾ inches wide.
A pair of flexible arcuate fins 30 and 32 extend upward from the upper end 22 of the tubular unit 20 . The arcuate fins 30 and 32 face each other, and are separated from each other by a slot 34 . Each of the fins 30 and 32 has a threaded section 36 on the outside thereof that is contiguous with the threaded section of the opposite fin. Each of the arcuate fins 30 , and 32 is about one inch high. The fins 30 and 32 have a certain degree of flexibility, enabling them to move inwardly in relation to pressure that may be applied on them. The entire tubular unit 20 is preferably made of a plastic material such as polyethylene or polycarbonate, but other suitable materials such as metal can be used also. The tubular unit 20 optionally has vertical ribs 37 on the outside thereof to give added strength, and a gripping surface for a user to grab onto when adjustment is to be made to the position of the slideable mechanism 18 on the mop handle 12 .
A wing nut 38 having interior threads 40 ( FIG. 2 ), and an outwardly extending horizontal flange 42 at the base thereof fits over the tubular unit 20 . It is secured to the tubular unit 20 by threading its threads 40 over the threads 28 at the lower end 22 of the tubular unit 20 . The threads 40 and the threaded section 28 are complementary to one another. The internal diameter of the wing nut 38 is slightly larger than the external diameter of the tubular unit 20 . In a preferred embodiment, the wing nut 38 is 1⅝ inches tall, and the flange 42 extends about 1 inch horizontally. The external diameter of the wing nut is 1⅞ inches, while the internal diameter of the wing nut is 1 9/16 inches. It is preferably made of the same plastic material as the tubular unit 20 .
A locking nut 44 with internal threads 46 fits over the fins 30 and 32 , and is fastened to the tubular unit 20 by threading it over the threads 36 on the fins 30 and 32 . In a preferred embodiment, the locking nut is about 1 7/16 inches high. The internal diameter of the locking nut 44 is greater at the bottom than at the top. In a preferred embodiment, it has an internal diameter at its bottom of 1⅜ inches, and an internal diameter at its top of about 1 inch. Thus when the internal threads 46 of the locking nut 44 engage the threads 36 on the flexible fins 30 and 32 , continued screw action and the reduced diameter of the locking nut 44 at the top thereof, forces the fins 30 and 32 inward to engage the mop handle 12 , thus securing the slider mechanism 18 in a fixed position on the handle 12 of the mop 10 . When it is desired to move the slider mechanism 18 , the locking nut 44 is released, or loosened, and the slider mechanism 18 repositioned to another desired position on the handle 12 .
The slider mechanism 18 portion of this invention can be made of any suitable material, but is preferably made of plastic. Polyethylene is the preferred plastic material. Other material, such as aluminum can be used, but plastic is cheaper, and more easily molded, and so is the preferred material.
The second component of the mop shield 16 of the invention is a cover 48 which is secured to the slider mechanism 18 , as seen in FIG. 4 . As seen in FIGS. 3 and 4 , the cover 48 is rectangular in shape, and is formed like an envelope, having front 50 and back sides 52 , a closed top 54 , and an open bottom 56 . The cover 48 has an opening 58 in the top through which the shaft of a mop handle 12 can be inserted. The opening 58 has to be sufficiently large so as to enable it to pass over the tubular unit 20 without damage. The cover 48 optionally has a zip lock configuration 60 adjacent the open bottom 56 , so as to enable the bottom 56 to be closed, thus insuring complete enclosure of the mop head 14 if desired.
In a preferred embodiment, the cover 48 is 18 inches tall, 13 inches wide, and is made of 6 mil thick, clear plastic sheeting. If desired, the specific room or area for which the mop is to be used can be marked on the plastic sheeting with a suitable marking device.
The cover 48 is mounted on the slider mechanism 18 by first positioning the tubular unit 20 on the handle 12 of the mop 10 , at a desired location, then inserting the handle 12 through the open bottom 56 of the cover, then the opening 58 at the top of the cover 48 , and bringing the cover 48 down so that the inside surface of the cover 48 at the top thereof, rests on the horizontal wings 26 of the tubular unit 20 . See FIG. 4 . Next, the wing nut 38 is screwed down on the threads 28 of the tubular unit 20 , simultaneously pressing down on the top external surface of the cover 48 , and fixing the cover 48 in position. That is, as seen in FIG. 4 , the cover 48 is fastened in position between the flanges 42 of the wing nut 38 and the wings 26 of the tubular unit 20 . Following this, the locking nut 44 is put into place by screwing it onto the threads 36 of the fins 30 and 32 .
The position of the slider mechanism 18 on the mop handle 12 can be adjusted by loosening the locking nut 44 , moving the slider mechanism 18 to the desired position, then tightening the locking nut 44 again. See FIG. 7 . As previously stated, tightening the locking nut 44 forces the fins 30 and 32 inward to press on the handle 12 , thus fixing the mop shield 16 in place.
FIG. 5 shows the position of the mop shield 16 of this invention in a raised position, and FIG. 6 shows it in the lowered position with the cover 48 surrounding the mop head 14 . The position of the mop shield 16 of the invention can be adjusted on the mop handle 12 as desired. Thus, as previously stated, the invention is a mop upon which is mounted the mop shield described herein.
It will be understood by those skilled in the art that various modifications can be made in the mop and mop shield of the invention without departing from the spirit and scope of the invention. | A mop and mop shield or cover is described in which the mop shield is slideably mounted on the handle of a mop, and capable of being lowered over the head of the mop to protect it from damage. The protective shield can also be marked, so as to enable a person to identify the purpose for which the mop has been used. | 0 |
FIELD OF THE INVENTION
The present invention is related to a device and a high-speed receiver including such a device, which can for instance be used for communication of serial binary data over a copper line, according to the Low Voltage Differential Signalling method.
STATE OF THE ART
Low Voltage Differential Signalling (LVDS) is a method for high-speed serial transmission of binary data over a copper transmission line. It is widely adopted in telecom equipment requiring high bandwidth data and clock transfer because of its immunity to crosstalk noise, low electromagnetic interference and low power dissipation. As telecom and networking systems move towards multi-Gb/s rates, maintaining adequate signal integrity becomes the bottleneck for system expansion. The use of optical interconnections is still limited due to their high cost, while copper transmission lines still provide a cost-effective alternative. The main cause of inter-symbol interference in the high-speed serial links is the attenuation and the dispersal of frequency components resulting from the signal propagation down a transmission line. Data pulses respond to these effects with a loss of amplitude and displacement in time. This results in signal skew (jitter) at the input of the receiving LVDS device, increasing the bit error rate of the link. In the Gb/s range the deterministic jitter occupies a significant part of the receiver input data eye for typical interconnection lengths, setting hard requirements for the LVDS receiver in terms of jitter contribution. The increasing number of backplane interconnections significantly increases the board crosstalk noise. The power supply interference is another concern since the number of serial links per ASIC is continuously increasing.
The original LVDS standard ANSI/TIA/EIA-644 specifies rail-to-rail common-mode range of the receiver. Although the common-mode disturbance might have lower amplitude, it is important to guarantee full common-mode range and good common-mode rejection. Since the original LVDS standard was defined for 2.5V devices and lower bit rates, it is impossible to design a fully compliant LVDS transceiver in a state-of-the-art 1.2V process.
A common technique allowing rail-to-rail common-mode range is the use of complementary NMOS-PMOS input stages with overlapped active regions. Although a 1.2V digital CMOS process is convenient for high-speed designs, it puts limitations on the number of MOS devices stacked between the supply rails.
The closest prior art solution, as described in patent EP 1 067 691 A1, will experience problems at a supply voltage of about 1V (used in 0.13 μm CMOS technologies), because the presence of the current source in the prior art embodiment gives in the transistor implementation an additional level in the number of stacked devices (at least 3). Moreover, this transistor level implementation of the current source is difficult in a low-voltage process when none of the current source terminals is grounded. The current source implementation would add additional capacitive load to the circuit nodes, reducing the speed and increasing the data dependent jitter. It would also cause variation of the differential gain and propagation delay at different common-mode levels.
The prior art solution requires a high-speed voltage comparator to be used together with two identical input stages. Furthermore, the prior art implementation is relatively complex in terms of numbers of transistors required.
Aims of the Invention
The present invention aims to provide a receiver structure that does not have the drawbacks of the state of the art. It also aims to provide a receiver structure, which can be processed in advanced technologies (requiring a low supply voltage), while at the same time being simple and solving the problems of speed, reduced dynamic range, and differential gain.
SUMMARY OF THE INVENTION
The present invention is related to a device comprising, between a differential pair of inputs, consisting of a first input and a second input, and an output, a differential pre-amplifier. The device further comprises
an offset-reducing block cascaded with said differential pre-amplifier and arranged for reducing the offset generated by said differential pre-amplifier, and a buffering block in series with said offset-reducing block and arranged for amplifying and buffering the output voltage of said offset-reducing block.
In an advantageous embodiment the differential pre-amplifier comprises a first and a second half pre-amplifier, each of said half pre-amplifiers having a first and a second input and an output, the outputs of said half pre-amplifiers being coupled together to form an input to said offset-reducing block.
In a specific embodiment the first input of said first half pre-amplifier is coupled to a first input of said device, whilst the second input of said first half pre-amplifier is coupled to the second input of said device. The first input of said second half pre-amplifier is coupled to the first input of said device, whilst the second input of said second half pre-amplifier is coupled to the second input of said device.
Advantageously, the offset-reducing block comprises a transimpedance circuit, that preferably comprises a resistance and an inverter stage.
According to a specific embodiment the offset-reducing block additionally comprises means for equalisation. Said means for equalisation comprises a RC network.
In another embodiment the buffering block comprises means for amplification and pulse shaping.
In a specific embodiment the means for amplification and pulse shaping comprises an inverter circuit.
In a particular embodiment the invention relates to a receiver structure comprising a device as previously described.
SHORT DESCRIPTION OF THE DRAWINGS
FIG. 1 represents the prior art solution.
FIG. 2 represents the solution according to the invention.
FIG. 3 represents a first transistor level implementation of the invention.
FIG. 4 represents a second transistor level implementation including the optional equalisation.
DETAILED DESCRIPTION OF THE INVENTION
The prior art solution is shown in FIG. 1 and the structure of the invention in FIG. 2 . In the prior art, the pre-amplifier block was followed by a comparator for comparing two incoming voltages (outputs of both half amplifiers). In the present invention, such a comparator block is no longer present, but is replaced by an offset-reducing block followed by a buffering block. Such an offset-reducing block, in a preferred embodiment consisting of a transimpedance stage, is now adapted to reduce the offset originating from the previous stage consisting of two half-amplifiers, by forcing its sole input voltage being the output voltage of both output terminals of both amplifiers coupled together, to a fixed threshold. The buffering stage BB, in its most simple implementation consisting of an inverter INV, is performing amplification and pulse shaping.
The inputs INN and INP to the two ‘half amplifiers’ (HPA 1 p and HPA 2 p ) of the prior art are cross-connected in order to generate complementary output signals (i.e. with 180 degrees phase shift), while in the invention they are in phase. The outputs of both half amplifiers are separated in the prior art, whereas now they are coupled together.
Detailed embodiments of the device will now be described, with reference to FIGS. 3 and 4 . It is to be remarked that, although the figures depict implementations in a CMOS technology, embodiments in other technologies such as bipolar, BICMOS, III-V and other technologies are as well possible. In this case the MOS transistors depicted in FIGS. 3 and 4 are to be replaced by the appropriate bipolar or other active devices, as is well known to a person skilled in the art. In the remainder of this document, a MOS implementation will be described into more detail.
The receiver device structure according to the invention is designed for a low-voltage technology, such as an advanced CMOS technology. In such technologies the short-channel effect in sub-micrometer CMOS processes causes linearisation of the MOS quadratic characteristic, improving the similarity of the NMOS and PMOS I DS (V GS ) (drain current as function of the gate to source voltage) characteristics. Since the low supply voltage and the linear I DS (V GS ) characteristic limit the maximum drain current to practical values, it is possible to implement a grounded source input differential stage without additional current sources, improving the input dynamic range. An additional advantage of this structure is the fact that the required slew-rate is achieved with smaller W/L values (with W denoting width and L length), as more gate-overdrive voltage is available. Because the function of the input stage is conversion from differential input to single-ended ‘digital’ output, its most important parameter is the common-mode rejection. Once this conversion is done in a proper way, one can provide the necessary gain in the single-ended domain by simple inverters. It is important to maintain a low voltage gain in the input stage in order to avoid saturation memory effects, causing data dependent jitter. In the proposed simplified topology as shown in FIG. 3 , the input PMOS and NMOS stages have the property of rejecting the input common-mode component. The input transistors are scaled in such a way that the voltage at node N 1 is at nearly half-supply level, when the differential input component V inp −V inn =0 and the common-mode component 0<V CM <V DD .
An implementation of the offset-reducing block (ORB) consists of a transimpedance stage, including MN 5 , MP 5 and RP 1 . The stage is driven by the input current and generates an output voltage and is such that the feedback current generated by it is able to compensate the offset of both pre-amplifiers. Therefore the feedback current, determined by resistance RP 1 , the output current capability of the stage MN 5 -MP 5 and the gain of this stage, has to be high enough to compensate the output offset current of both half pre-amplifiers. The output offset may be caused by transistor mismatch. Note that the offset-reducing block (ORB) has a frequency dependent input impedance. The relatively low input resistance of the transimpedance stage also equalises the voltage gains at both sides of the current mirrors MN 3 , MN 4 and MP 3 , MP 4 so the channel length modulation in the mirrored currents is not degrading the receiver common-mode rejection.
Another specific feature of the invention is the fact that the input capacitance of the stage MN 6 -MP 6 reduces the high-frequency gain of the transimpedance stage MN 5 -MP 5 and thus increases its input impedance Z IN — TI :
Z IN_TI = R 1 - A CL ,
with A CL denoting the closed loop small signal gain of the transimpedance stage and R the resistance of the feedback resistor RP 1 .
The increase of Z IN — TI causes high-frequency peaking of the input stage gain. This is equivalent to bandwidth increase in comparison to the prior art. The increased bandwidth reduces the data dependent jitter generation and increases the maximum speed of the receiving device. This is also in contrast to the prior art, where the maximum bandwidth is lower.
As an option, the invention may easily include an enhanced equalisation, consisting of a frequency correction function in the frequency domain. An embodiment of such an implementation is shown in FIG. 4 , whereby the low-pass behaviour of the channel is compensated and the deterministic jitter is cancelled by the addition of the resistors RP 2 ,RP 3 and the capacitors C 1 and C 2 to the original transimpedance block OB of FIG. 3 . The resulting offset-reducing block is denoted OB′. This enhanced behaviour results in an output eye diagram opening wider than the input eye opening for deterministic jitter. The equalisation is implemented as transconductance degeneration in the transimpedance stage MN 5 -MP 5 . The degenerated small signal transconductance of the inverter comprising MN 5 -MP 5 is:
G mINV = 2 · g m 1 + g m · Z S
where Z s is the impedance of the RC source networks (C 1 , RP 2 and C 2 , RP 3 ) and g m is the transconductance of the transistors MN 5 , MP 5 if Z s =0. Because the impedance of these RC source networks is decreasing as frequency increases, the gain is proportional to the frequency. This frequency correction compensates the low-pass response of the channel and reduces the deterministic jitter at the output. Note however that other implementations than that proposed in FIGS. 3 and 4 can be envisaged.
The implementation of the invention is much more simple that the prior art one. It implies coupling serially as few devices as possible between the supply terminals in order to allow minimum supply voltage operation. Furthermore, the grounded source input structure avoids the creation of common-mode poles, leading to a lower variation of the differential gain and propagation delay on common-mode extremes and to an increased dynamic range. | The present invention is related to a device comprising, between a differential pair of inputs, a differential pre-amplifier (HPA 1 , HPA 2 ), an offset-reducing block (ORB) cascaded with said differential pre-amplifier (HPA 1 , HPA 2 ) and arranged for reducing the offset generated by said differential pre-amplifier, and a buffering block (BB) in series with said offset-reducing block (ORB) and arranged for amplifying and buffering the output voltage of said offset-reducing block. | 7 |
NATIONAL FILING UNDER 35 USC 371
This application is being filed as a US National stage under 35 USC 371 of PCT Application No. PCT/US10/37044, which was filed Jun. 2, 2010 and also claims the benefit of U.S. Provisional Application Ser. No. 61/183,263 filed Jun. 2, 2009, entitled “A Novel Method for Microbial Depletion in Human Blood and Blood Products Using Antimicrobial PhotoDynamic Therapy” by Gerhard Wieland et al., both of which are incorporated by reference herein.
BACKGROUND OF THE INVENTION
1. Field of the Invention
Present invention relates to the destruction, elimination and/or inactivation of pathogenic microbes in biological fluids. In particular, it relates to antimicrobial photodynamic laser therapy method and device to eliminate pathogenic microorganism in biological fluids such as blood and blood products.
2. Invention Disclosure Statement
The spread of blood borne diseases resulting from transfusion of contaminated blood or blood product is recognized as a major medical health problem. Blood is most commonly donated as whole blood by inserting a catheter into a vein and collecting it in a plastic bag (mixed with anticoagulant) via gravity flow. Thus collected blood is then separated into components. Aside from red blood cells, plasma, and platelets, the resulting blood component products also include albumin protein, clotting factor concentrates, cryoprecipitate, fibrinogen concentrate, and immunoglobulins (antibodies). Red cells, plasma and platelets can also be donated individually via a more complex process called aphaeresis.
The importance of blood transfusions is widely known, especially in cases of people who suffer major trauma such as car accidents or in many surgeries that could not be performed without transfusion support. Without enough blood in blood vessels due to acute or massive blood loss there is not enough pressure to push new blood to the tissues, causing organ death because of lack of oxygen. Blood transfusions may also be used to treat severe anemia or thrombocytopenia caused by blood diseases. Another condition requiring frequent blood transfusions is people suffering from hemophilia or sickle-cell disease. Depending on the disease requirements, whole blood or blood products such as fresh frozen plasma, platelet concentrates, red blood cell concentrates and others should be transfused. In any case, to prevent a hazardous recipient's immune reaction transfused blood should be compatible with the components of the recipient's body.
Blood transfusions can be life-saving but, as with any treatment, there are risks involved. Many viruses, parasites, bacteria and/or toxins may be present in human blood and if contaminated blood or blood products are not efficaciously inactivated or the contaminants are not properly eliminated prior to blood transfusion this may cause infectious diseases with high mortality rates. There is a risk that a given blood transfusion will transmit a viral infection to its recipient. The risks of acquiring hepatitis B virus (HBV), Human Immunodeficiency virus (HIV) or hepatitis C virus (HCV), via blood transfusion are a major health threat even in developed countries like the U.S.
Bacterial resistance against antibiotics makes an infection much harder to treat. Higher doses or stronger drugs may be required to control infections in such cases. In extreme cases, bacterial resistance can be fatal. Antibiotics are powerful bacteria-killing drugs that help our bodies regain the upper hand when a bacterial infection develops. Overuse of broad-spectrum antibiotics, such as second- and third-generation cephalosporins, greatly hastens the development of methicillin resistance.
Staphylococcus aureus a Gram Positive bacterium is one of the examples for ever increasingly resistant pathogens. It is to be found on the mucous membranes and the skin also in healthy people. It is extremely adaptable to antibiotic pressure. Resistant strains, also known by the name Methicillin-resistant Staphylococcus aureus (MRSA), are responsible for difficult-to-treat infections in humans. Since the strains often happen to be resistant to more than one antibiotic compound it may also be referred to as Multiple-Resistant Staphylococcus aureus.
Over a period of time the bacteria generally develop resistance to antibiotics. Along with the present chemical therapy methods; photodynamic therapy—a treatment method against cancerous cells, has been found to be effective in destroying a wide range of microbes. Photodynamic therapy is based on activation of photosensitizer by appropriate wavelength. Photoactivated photosensitizer generates singlet oxygen and free radicals responsible for destruction of abnormal cells. Various photosensitizers have been studied for their bactericidal effect on pathogenic microbes and were found to be effective.
There are many steps taken to obtain uncontaminated donor's blood, nevertheless the major treat comes from the undetected microbial agents which need to be inactivated before blood transfusion. Blood components can be contaminated during any of the many steps of preparation like blood collection, processing, pooling and transfusion. Thus, tested donor's blood apparently healthy might be contaminated with millions of undetected/unknown infectious microbes. Furthermore, donor's blood units may be contaminated by bacteria during storage which will cause potentially fatal infections in the recipient; or may contain remained leukocytes which then release chemicals causing disease or severe fever.
In U.S. Pat. No. 5,660,731, Piechocki, et al. disclose a method, system and device for removal of methylene blue from biological fluid after anti-microbial treatment. In this patent they disclose a treatment protocol using methylene blue for inactivating materials such as virus and bacteria from blood and blood products. It is also discloses the method of separating the methylene blue from the biological fluid using carbon fibers.
Wollowitz, et al. in his U.S. Pat. No. 6,686,480 discloses how Psoralen compounds are used to form covalent crosslinks to the nuclei acid of pathogen for photo-decontamination of pathogen present in blood.
U.S. Pat. No. 5,545,516 by Wagner discloses methods of inactivating pathogenic contaminant in whole blood, plasma, cellular blood components using phenthiazin-5-ium dye(s) and irradiating at 560-800 nm to inactivate all the pathogens.
In U.S. Pat. No. 7,407,948; Griffiths et al. disclose a photosensitive composition named Phonoselenazinium and its use in photodynamic therapy as anti-infective, anti-cancer and sterilizing agent. In one of the embodiments he discloses the use of this composition for inactivating S. aureus, E. coil and other microbes under in vitro conditions by administering the required dosage of photosensitizer and irradiating the cells, after incubation, with a 665 nm CeramOptec diode laser.
U.S. Pat. No. 6,843,961 (Hlavinka et al.) discloses a PDT method and apparatus for inactivating contaminants in blood and blood products using photosensitizers and light of suitable wavelength.
In U.S. Pat. No. 7,244,841, Love et al. disclose use of a composition for killing or attenuating the growth of microorganisms by a method which does not comprise exposing the composition to photodynamic therapy light or sonodynamic therapy ultrasound source. The stimulation of the compound is innate.
An entirely different and promising approach is phage therapy. Wilson in his US Application Publication No. 2007/0020241 discloses a composition comprising of a photosensitizer and a bacteriophage. The bacteriophage used as targeting agent is staphylophage. The bacteriophages are conjugated to photoactive agents, which then target the bacteria specifically. The invention is useful to inactivate staphylococci, more particularly MRSA, EMSA, VRSA, hetero-VRSA, VISA or CA-MRSA strains. The phage therapy is a more complicated system. In U.S. application no. 2002/0001590 Kelly et al. use bacteriophages with antibacterial agents like antibiotic and chemotherapeutic agents to inactivate the pathogens.
Sowemimo-Coker et al. in U.S. Pat. No. 6,235,508 disclose a method of inactivating viral and bacterial contaminants using a composition having photosensitizers attached to a blocking agent and at least one halogen substituted or one non-hydrogen bonding ionic moiety or both. The preferred two photoactive compounds are psoralen and coumarin which are made to target the nucleic acid of viri specifically and bind to DNA and RNA covalently after irradiation with UV light or ionizing radiation leading to inactivation of the pathogens. The use of low toxic compounds along with PS and ionizing radiation can be harmful. Psoralens, are photoactive DNA-intercalating compounds and do not produce singlet oxygen.
In U.S. Pat. No. 6,323,012 Ben-Hur et al. disclose a PDT method for treating viral infection by administering 5-aminolevulinic acid to viral infected cells. After a short duration red light is applied to photodynamically activate protoporphyrin IX accumulated in viral infected cells.
In U.S. Pat. No. 7,094,378 Goodrich et al. disclose a method and apparatus for treating and inactivating microorganisms present in biological fluids. The method involves adjusting the percentage of plasma in the fluid to be treated and mixing with photosensitizer (riboflavin) and exposing the fluid to light whereby the microbes are inactivated. Similarly Hlavinka et al., in their U.S. Pat. No. 7,077,559 disclose a mixing system, apparatus and method for pathogen reduction in blood and blood products using riboflavin and light. The squeezing or clamping devices ensure proper photo-irradiation of blood and blood components.
Reddy et al in their U.S. Pat. No. 7,049,110 disclose a PDT method and apparatus for inactivating microorganisms in biological fluids by adding non-toxic PS to the fluid and exposing the fluid to photo-irradiation.
The conventional screening and processing methods used against pathogenic microbes are not found to be very effective in controlling its rapid transmission through contaminated blood and blood products. The method disclosed in prior art for elimination of microbes is not found to be effective in attenuating all the bacterial, viral and other pathogens as claimed. Thus, it is essential to eliminate or inactivate these pathogen materials from blood and blood products before transfusion. Unfortunately, up to now there have been many difficulties to eliminate or inactivate blood pathogens in materials from blood or blood products due to insufficient filtration capacity of devices, antibiotic resistance of difficult-to-treat microbes or lack of an efficient and efficacious device and/or method. Thus, there is a need to provide an efficient and efficacious method and device to eliminate or inactivate pathogenic material from blood and blood products, from single donors without damaging the therapeutic and biological properties of such biological fluids.
OBJECTIVES AND BRIEF SUMMARY OF THE INVENTION
It is an objective of the present invention to provide an Antimicrobial Photodynamic Therapy method and a treatment device for elimination destruction, and/or inactivation of pathogenic microbes to be found in biological fluids such as blood and blood products collected from donors.
It is another objective of the present invention to provide Antimicrobial Photodynamic Therapy method and a treatment device for purification of infected blood and blood products using an effective antimicrobial photosensitizer and light.
It is yet another objective of the present invention to provide an Antimicrobial Photodynamic Therapy method and treatment device having an illumination unit with light source for elimination of undetected viral component contaminating blood and blood products.
It is still another objective of the present invention to provide an Antimicrobial Photodynamic Therapy method and treatment device for eradiation, elimination and/or inactivation of pathogens without altering or affecting the biologic and therapeutic properties of the treated blood and blood products.
It is also an objective of the present invention to provide an antimicrobial photodynamic laser therapy method and device to kill, eliminate and/or inactivate pathogenic material in whole blood and blood products like human fresh frozen plasma, thrombocyte concentrates, red blood cells (RBC) and blood clotting factors (V, VII, IX, X and XIII).
It is also another objective of the present invention to provide suitable light sources having appropriate wavelength to induce the production of singlet oxygen. Possible light sources are chosen from a list comprising of diode laser systems, high power LEDs, white light or other light sources emitting visible light, and even light sources emitting light in near-UV or near-IR.
Briefly stated, innovative treatment methods and devices for attenuating/inactivating the pathogenic microbes found in biological fluids such as blood and blood products including human single-donor-fresh-frozen-plasma, platelet concentrates, red blood cells (RBC), blood clotting factors (e.g. factors V, VII, VII, IX, X and XIII) are provided. An Antimicrobial Photodynamic Therapy method is used to eliminate multiple (resistant) bacteria, viral agents, fungi, parasites and other undetected or non-easily detected pathogenic microbes or particles in blood and blood products without affecting their biological properties. The resistant bacteria are difficult to be eliminated. This is especially true for S. aureus and related strains, Staphylococcus epidermidis or Propionibacterium acnes, Borrelia species and other bacteria found on skin. Further embodiments of the present invention eliminate undetected or non-easily detected viral agents contaminating blood and blood products, which are responsible for spreading hepatitis, Acquired Immune-Deficiency Syndrome (AIDS) and other blood borne viral diseases. Human Immune-deficiency Viruses (HIV), hepatitis B and hepatitis C viruses have recently emerged as major blood borne infections. Numerous parasites transmitted through blood and derived products are also eliminated by these novel processes and devices.
The above and other objects, features and advantages of the present invention will become apparent from the following description read in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF FIGURES
FIG. 1 depicts a top view of a four-fold illumination unit having four LED-ring units.
FIG. 2 illustrates an embodiment of an illumination unit with two LED-rings and an illumination bag having connector.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
There are many blood borne, transfusion transmitted and related diseases. Present invention provides an Antimicrobial Photodynamic Therapy method and device for effective elimination, reduction and/or inactivation of pathogenic microorganisms to be found in whole blood and blood products. Whole blood content including red blood cells (RBC), white blood cells (WBC) and platelets are suspended in a fluid called plasma. The terms ‘microorganism’, ‘pathogen’, ‘microorganism’, ‘microbial agents’ or ‘microbe’ in this invention include all types of harmful or blood contaminating bacteria and their resistant species, prions, fungi, viri, protozoan and blood parasites causing severe infections in both humans and animals. The terms “blood products” and “blood components” refers to human single-donor-fresh-frozen-plasma, thrombocyte concentrates, platelet pheresis, red blood cells (RBC), white blood cell (WBC), granulocyte concentrates, albumin, cryoprecipitations, antithrombin III, antihemophilic factor (AHF), blood clotting factors (e.g. factors V, VII, VII, IX, X and XIII) and combinations of them. The terms “biological fluid” or “body fluid” refers to whole blood or blood products.
The development of resistances to antibiotics is the major problem faced while treating bacterial infections. Especially multiple-resistant bacteria for e.g. methicillin-susceptible Staphylococcus aureus (MSSA) and methicillin-resistant Staphylococcus aureus (MRSA) are the most frequently identified antimicrobial drug resistant pathogens in US hospitals. At the same time the real threat in blood donated from apparently healthy donors is corning from skin bacteria like Staphylococcus epidermidis or Propionibacterium acnes, Borellia species and other pathogenic bacteria transmitted in the process of blood donation. The present invention provides a method and device to eliminate such bacterial infesting of biological fluids.
Transfusion Transmitted Virus is a relatively new virus found to contaminate blood. Viral agents like herpes viri, Human immunodeficiency virus (HIV), Hepatitis C virus (HCV) and Hepatitis B Virus (HBV) are found in blood and often go undetected. Other lesser known viral agents include T-cell lymphotropic viruses, cytomegalovirus, and parvovirus. Virus infected blood then is responsible for transmission of blood borne diseases like AIDS, Hepatitis and similar. Eliminating such undetected viri, resistant bacteria and other microbes in biological fluids such as blood and blood products is made possible using the method and device of present invention.
Present invention also aims to eliminate infectious blood-borne protozoan parasites like Trypanosoma cruzi , which causes Chagas' disease; the Trypanosoma species causing African sleeping sickness; plasmodium species causing malaria, and especially Plasmodium falciparum which is responsible for malignant and increasingly drug resistant type of malaria. In addition to this threat, there are also other unknown microbes yet to be identified. The aim in general is to destruct the non-easily detected hazards in blood donated by healthy donors.
Photosensitive agents and their derivates are effectively used as an antimicrobial agent. A preferred photosensitizer, discovered herein, is Safranin O which exists in two tautomeric forms and can be photo activated at 532 nm.
Safranin O exhibits high antimicrobial activity. Safranin O is found to be very effective even in the presence of complex biological fluids like blood, serum etc. While other photosensitizers are used as antimicrobial agents, in the present invention the preferred photosensitizer is selected from the group of phenothiazines, porphyrins, chlorins and others.
In one embodiment, a treatment device for antimicrobial photodynamic therapy comprising an illumination unit, sterile light-transparent container bag(s) and bag holder(s); and a photosensitizer-absorber unit is provided. The illumination unit of the present invention includes light source selected from the group consisting of, but not limited thereby to lasers, diode laser systems, LEDs, high power LEDs, lamps, white light or other light sources having one or more wavelengths absorbed by the selected photosensitizer. The light source operates at appropriate wavelengths including the visible light, near-Ultraviolet (UV) and/or near-Infrared (NIR) region of the electromagnetic spectrum (EMS). The illumination unit uses the light source to induce the production of singlet oxygen while performing the photodynamic therapy. Preferably, the light source comprises LED lamps. Illumination unit further comprises a cooling element and boxes as bag holder(s). Additionally, the illumination unit consists of means for sliding, rotating or a similar action, ensuring proper mixing and exposure of the blood within the container bag to light from illumination unit. It is also well equipped to hold the sterile light-transparent container bag in place during the procedure. The container bag containing blood to be placed in the illumination unit is photo-transparent to allow penetration of light to activate the photosensitizer. Thus, before illumination is performed container bag containing blood is properly covered to avoid early photosensitizer activation. Preferably, sterile light-transparent container bags are connected with the aid of serial or parallel tubes to provide the appropriate illumination dose to the treated biological fluid. The photosensitizer-absorber unit is used to remove the excess, un-reacted or non-activated photosensitizer present in the treated biological fluid. In one embodiment, the photosensitizer-absorber unit consists of a housing filled with porous beads and sponges which extract and/or absorb the excess of or non-activated photosensitizer from treated blood and blood products. Treated and cleansed blood and blood products can be stored for further use.
In another embodiment, an antimicrobial photodynamic therapy (PDT) method for the elimination, eradication and/or inactivation of pathogens from blood and blood products without adversely affecting the essential elements of their biological activity comprises the steps of: 1) collecting blood; 2) separating whole blood in blood components if necessary; 3) mixing a photosensitizer with blood or blood components comprising a treatment fluid; 4) illuminating said treatment fluid; 5) depleting excess and/or non-activated photosensitizer and residual fragments; and 6) collecting and storing the treated and cleansed blood or blood components in a sterile fashion until further use.
In order to prevent blood clotting an anti-coagulation substance like heparin or citrate is added to the collection bag. Preferably, blood and blood components are collected from healthy donors. A centrifuge may be used to hasten the separation step. Separated blood components are then placed into sterile bags and stored, ready for subsequent antimicrobial PDT treatment. Preferred photosensitizer is BLC 2003 (Safranin-O). The existence of an incubation period after or during step 3) ensures a proper mixing of photosensitizer with blood or blood components to be treated. Additionally, a sliding, rotating or similar motion provided by the treatment device allows further mixing between the photosensitizer and blood or blood components and completely illumination of the biological fluid and/or its components. Illumination step is performed with the light source of the treatment device of wavelength coded to the selected photosensitizer is employed. When the photosensitizer used is BLC 2003 the light source preferably operates/includes at 532 nm. The step of depletion of excess and/or non-activated photosensitizer and residual fragments may be done by passing the active microbe-free treatment fluid through a photosensitizer-absorber unit which may also adsorb or absorb residual fragments such as inactivated microbes and alike. Treated blood or blood components may be re-mixed and re-infused into a human or animal fluid stream adjusting all necessary parameters such as temperature, density, composition and others.
The antimicrobial PDT method of present invention does not adversely affect the essential elements of the biological activity of the treated blood or blood products nor shows impairment of their functional capacity after treatment.
The present invention is further illustrated by the following examples, but is not limited thereby.
Example 1
General Treatment Procedure for Microbial Elimination from Blood and Blood Products
The general steps for elimination eradication and/or inactivation of pathogens from blood and blood products involves:
Step 1: Involves collection of blood from a healthy donor. Anti-coagulant like heparin or citrate is added to the collection bag to prevent clotting of blood.
Step 2: Separation of the blood components. Blood components include red blood cells, plasma, platelets, and (cryo-precipitated) anti-hemophilic factors (AHF). If blood is treated to prevent clotting and permitted to stand in a container, the red blood cells, which weigh more than the other components, will settle to the bottom; the plasma will stay on top; and the white blood cells and platelets will remain suspended between the plasma and the red blood cells. A centrifuge may be used to hasten this separation process. The platelet-rich plasma is then removed and placed into a sterile bag and can be used to prepare platelets and plasma or cryoprecipitated AHF. To obtain platelets, the platelet-rich plasma is centrifuged, causing the platelets to settle at the bottom. Plasma and platelets are then separated and made available for transfusion. The plasma also may be pooled with plasma from other donors and further processed, or fractionated, to provide purified plasma proteins such as albumin, intravenous immuno-globulin (IVIG), and clotting factors.
Step 3: The sterile light-transparent container bags containing blood and blood products are infused with photosensitizer preferably BLC 2003 (Safranin-O).
Step 4: Ensure proper mixing of photosensitizer and blood and blood products followed by a short incubation period.
Step 5: The sterile light-transparent container bag, containing blood or blood products mixed with photosensitizer, is placed into the treatment device having a bag holder which can be moved in sliding motion. Once the bag is secured to the holder, holder is set into sliding motion. This ensures completely irradiation of blood and its components within the sterile light-transparent container bag.
Step 6: Irradiation at a wavelength (532 nm when BLC2003 is used) coded to the selected photosensitizer.
Step 7: The microbe free fluid then is passed through a photosensitizer-absorber. This absorber unit removes the excess and non-activated photosensitizer present in the treated biological fluid.
Step 8: The cleansed and treated blood/blood component is collected and stored until further use.
Thus treated blood shows neither significant decrease in coagulation factor activities nor is the functional capacity of plasma affected. Present invention can be employed to inactivate pathogens at blood banks, in hospitals or labs.
Example 2
Treatment Device and Antimicrobial PDT Method to Treat Blood and Blood Products
FIG. 1 depicts the top view of a four-fold illumination unit 100 with four LED-ring units 101 on four sides of the rectangular cubical shaped illumination unit. The four LED units are located on cooling element 103 in the centre and having the corresponding boxes 105 containing the sterile light-transparent container bags. The sterile light-transparent container bags are connected by tubes in order to obtain a flow through all four bags and a four-fold illumination LED unit. Each inflow for the sterile light-transparent container bag is located at the bottom side. FIG. 2 shows how each illumination unit is arranged with corresponding sterile light-transparent container bag on each side of four-fold illumination unit 100 .
FIG. 2 shows LED unit and the corresponding arrangement of the box and sterile light-transparent container bags to be illuminated within each side of illumination unit 200 . Each of the LED units has arrays of high powered LEDs arranged in two concentric rings 201 (Luxeon® Rings with total 18 LED-units with a LED wavelength of 530 nm, when the preferred photosensitizer is used). The arrangement of LEDs can be done in one or more rings and in many different ways. The illumination unit has a corresponding box wherein illumination bag 203 is located, having tube connectors 205 . The arrows indicate the flow direction of bacterial suspension.
The infected whole blood from the healthy donor is withdrawn and collected into a sterile citrate or heparin sterile light-transparent container bag. The sterile light-transparent container bag in this invention is specially designed for the illumination unit to be used during antimicrobial photodynamic therapy treatment. Thus collected blood is separated to its respective components by methods already known in the prior art and to the experts in the field or the whole blood as such can be subjected to present treatment method. The photosensitizer agent is added into the photo-transparent sterile bag. The added photosensitizer is mixed to the blood and/or blood components using an orbital shaker to ensure complete exposure of the microbes to photosensitizer. Thus prepared blood bag is now placed into a bag holder found within the illumination unit.
Once the bag is secured into the holder, it is set into a sliding motion. The illumination unit is switched on and the sterile light-transparent container bag in sliding motion is exposed to a specific wavelength matching the absorption spectrum of photosensitizer added for normally prolonged time sufficient to eliminate bacterial and parasitic particles. The photosensitizer accumulates on and in the microbial cells which subsequently are destroyed by a photo-cytotoxic effect. The treated fluid is allowed to pass through a photosensitizer-absorber unit consisting of plastic housing that is filled with tiny porous beads and larger sponges. These beads/sponges extract/absorb the excess of or non-activated photosensitizer from the treated fluid. The excess or unreacted photosensitizer in the treated blood is finally removed. The cleansed blood and blood products can be stored for further use. Thus treated blood and its products are still intact in their biological function and their therapeutic effect is not reduced. The present method and device use in this invention is effectively used to eliminate the microbial pathogens.
This method can be use to eliminate pathogens in biological fluids, which includes but is not limited to whole blood, blood products, and blood components; the term blood component further includes human single-donor-fresh-frozen-plasma, platelet concentrate, red blood cells (RBC), blood clotting factors (e.g. factors V, VII, VII, IX, X and XIII) individually or in combination.
Example 3
Purification and Elimination of Undetected Viral Agents from Donated Blood
Blood transfusions can be life-saving in some situations, such as massive blood loss due to trauma, or can be used to replace blood lost during surgery. Blood transfusions may also be used to treat a severe anemia or thrombocytopenia caused by a blood disease. People suffering from hemophilia or sickle-cell disease may require frequent blood transfusions. Early transfusions used whole blood, while modern medical practice uses only components of the blood. Donated blood is usually subjected to processing after it is collected, to make it suitable for use in specific patient populations. In a number of infectious diseases such as HIV, syphilis, hepatitis and others undetected microbes can be passed from the seemingly healthy blood donor to recipient through blood transfusion. The present invention helps to eliminate undetected or non-easily detected viral agents and provides biological fluids free of pathogenic microbes for safe use. The whole blood collected from patient is mixed with a minuscule amount of a non toxic photosensitizer, preferably Safranin O. The sterile light-transparent container bags containing whole blood and Safranin O is thoroughly mixed using an orbital shaker and placed into a bag holder in illumination unit, set into sliding motion. The illumination unit is provided with light source having a wavelength 532 nm. The light source used can include a laser or high-power LED-light. Light sources emitting light at visible region, near UV and/or near IR can be used in the illumination unit, depending on the absorption characteristics of the selected photosensitizer. Thus bags containing treated blood should be stored in climate controlled chambers until final use in hemodiafiltration/or for other purposes. This normally prolonged time should be sufficient to eliminate viral particles. The excess or non-activated photosensitizer in the treated blood and blood products is removed using photosensitizer-absorber unit/means consisting of plastic housing that is filled with tiny porous beads and larger sponges. These beads extract/absorb the excess or non-activated photosensitizer molecules from the treated biological fluid.
Example 4
Purification and Elimination of Parasites from Donated Blood
Generally considered healthy person's blood may also be contaminated by pathogenic microbes growing under storage conditions especially in platelet concentrates stored at 37° C. The blood has nutrients, sugars, oxygen, providing the perfect environment and temperature for the growth of microorganisms. If the immune system is healthy, parasites are kept in check. The most common protozoan parasites found in blood includes endo-parasites, such as the malarial parasites and trypanosomes, having their infective stages in the host's blood. General known protozoa are Plasmodium species causing malaria, another protozoon, Trypanosoma cruzi , causing Chagas disease, or American sleeping sickness, and Trypanosoma brucei causing African trypanosomiasis. These parasites are found in the blood supply in increasing numbers. The parasites enter fat and muscle cells and begin to multiply, eventually being released into the blood and thus distributed throughout the body. They eventually become quite rare in the blood, but continue to live and multiply in organs. The infection persists indefinitely with live and infectious parasites in both blood and organs. Parasites can be passed on when the bug bites again, this time taking in parasites with its meal and subsequently passing them on to the next person it bites. Parasites can also be passed on via blood transfusions or organ donations. Present invention is effectively employed to eliminate such parasites from blood and blood products making them safe for further use in hospitals and blood banks. The blood collected from the healthy donor is infused with Safranin O, a photosensitizer which can target and after illumination inactivates parasites in the blood fluid. Sterile light-transparent container bag containing the photosensitizer and blood is now placed into an illumination chamber. The bag holder is set into sliding motion to ensure thorough exposure of the bag with blood and photosensitizer to light. The blood and its components are not damaged. The unreacted and any excess photosensitizer in the blood is removed, which is now safe for further use in patients.
The treatment method and device of present invention can be employed to treat either the whole blood, or separated blood components individually as described in the general procedure in example 1.
Having described preferred embodiments of the invention with reference to the accompanying drawings, it is to be understood that the invention is not limited to the precise embodiments, and that those skilled in the art can effect changes and modifications without departing from the scope of the invention as defined in the appended claims. | Treatment methods/devices are provided for attenuating/inactivating the pathogenic microbes found in biological fluids e.g. blood/blood products including human single-donor-fresh-frozen-plasma, platelet concentrate, red blood cells, blood clotting factors. An Antimicrobial Photodynamic Therapy method is used to eliminate multiple (resistant) bacteria, viral agents, fungi, parasites and other undetected or non-easily detected pathogenic microbes or particles in blood and blood products without affecting their biological properties. Resistant bacteria are difficult to be eliminated. This is especially true in the case for S. aureus and related strains, Staphylococcus epidermidis or Propionibacterium acnes, Borrelia species and other bacteria found on skin. Further embodiments eliminate undetected or non-easily detected viral agents contaminating blood/blood products responsible for spreading hepatitis, Acquired ImmunoDeficiency Syndrome and other blood borne viral diseases. Human Immunodeficiency, hepatitis B and hepatitis C viruses have emerged as major blood borne infections. Numerous parasites transmitted through bloods and derived products are also eliminated by these processes/devices. | 0 |
FIELD
[0001] This description relates to an organization device, system, and method for organizing and/or managing one or more cards.
BACKGROUND
[0002] Various organization devices for managing cards, such as credit cards, have been developed. For example, wallets have one or more holders for placement of credit card for organization purposes. There is a need for improvements in organization devices, systems, and method for managing one or more cards.
BRIEF SUMMARY
[0003] An organization aid device which permits efficient identification, management, and/or access to credit card, debit cards, and other card-like devices from each other and/or within a carrier for carrying card-like devices is described.
[0004] An organization aid carrier device for convenient packaging of the organization aid devices is described.
[0005] An organization system which wherein a plurality of organization aid devices are used for efficient identification, management, and/or access to credit card, debit cards, and other card-like devices from, for example each other and/or with a carrier for carrying the card-like devices, is described.
[0006] An organization method for efficient identification, management, and/or access to credit card, debit cards, and other card-like devices from each other and/or within a carrier for carrying card-like devices is described.
[0007] A method of manufacturing the organization aid device and/or organization aid carrier device is described.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIG. 1 a shows a front-side view of an embodiment of the organization aid device and an embodiment of the organization aid carrier device.
[0009] FIG. 1 b shows a back-side view of an embodiment of the organization aid device and an embodiment of the organization aid carrier device.
[0010] FIG. 2 shows a close up portional view of an embodiment of the organization aid carrier device, wherein an embodiment of the organization aid device is being separated from the organization aid carrier device.
[0011] FIG. 3 shows a close up portional view of an embodiment of the organization aid device, wherein a removable layer is being removed exposing an adhesive layer.
[0012] FIG. 4 shows an example of a card having two organization aid devices attached thereto.
DETAILED DESCRIPTION
[0013] An embodiment of the organization aid device 100 has a flat front side, a flat back side, wherein at least a portion of the back side surface includes an adhesive layer 200 . As shown in FIG. 3 , a removable layer 201 may be placed on top of the adhesive layer 200 to protect the adhesive layer 200 from unwanted attachment of the organizational aid device. The removable layer 201 is readily removable such that the removable layer 201 is removed prior to attaching the organization aid device 100 to a card-like device.
[0014] A card-like device includes, but not limited to, a credit card 300 , an identification card, a business card, a security card, a RFID card, a passport, and other card-shaped devices.
[0015] The card-like device has a length and a width. As used herein, the length of the card-like device is longer than the width of the card-like device. Accordingly, as used herein, the credit card 300 has a length and a width, wherein the length is longer than the width.
[0016] As used herein, the card-like device includes, but is not limited to, a device that follow the international standards that defines the physical characteristics for card-like devices, such as for example, ISO/IEC 7810, ISO/IEC 7813, ISO/IEC 7811, and/or ISO/IEC 7816. Accordingly, the card-like device may have dimensions according to ID-1, ID-2, ID-3, or ID-000. A card-like device according to ID-1 has dimensions of 85.60 mm×53.98 mm. A card-like device according to ID-2 has dimensions of 105 mm×74 mm. A card-like device according to ID-3 has dimensions of 125 mm×88 mm. A card-like device according to ID-000 has dimensions of 25 mm×15 mm.
[0017] As used herein, the credit card 300 includes any card-like device used in financial transactions, such as for example, but not limited to, bank issued credit cards, merchant issued credit cards, charge cards, debit cards, government-issued payment cards, pre-payment cards, cash cards, and/or gift cards. The credit card 300 may follow ISO/IEC 7813 which defines additional characteristics of ID-1 banking cards, for example having dimensions of 85.60 mm× 53 . 98 mm, a thickness of 0.76 mm, and corners rounded with a radius of 3.18 mm.
[0018] An embodiment of the organization aid device 100 is smaller than a credit card 300 . An embodiment of the organization aid device 100 has a width that is less than or equal to the length of a credit card 300 . An embodiment of the organization aid device 100 has a length that is less than or equal to the width of a credit card 300 . In an embodiment, shown in FIGS. 1 a and 1 b, the organization aid device 100 has a width of about 1 / 6 of the length of the credit card 300 . In the embodiment, shown in FIGS. 1 a and 1 b, the organization aid device 100 has a length that is about ½ the width of the credit card 300 .
[0019] An embodiment of the organization aid device 100 is smaller than a card-like device that is being organized. In an embodiment, the organization aid device 100 has a width that is about ⅙ of the length of a card-like device. In the embodiment, the organization aid device 100 has a length that is about ½ the width of a card-like device.
[0020] An embodiment of the organization aid device 100 includes a tab. In an embodiment, the tab has a width that is less than or equal to the width of the organization aid device 100 . In an embodiment, the tab has a width that varies, for example by having rounded corners.
[0021] In an embodiment, shown in FIGS. 1 a and 1 b, the organization aid device 100 has a tab having a width of about ⅙ of the length of a credit card 300 . In the embodiment, shown in FIGS. 1 a and 1 b, the organization aid device 100 has a tab having a length that is less than ½ the width of a credit card 300 .
[0022] An embodiment of the organization aid device 100 includes an indicator 400 . In an embodiment, the indicator 400 is on the tab. In an embodiment, the indicator 400 is on a major surface of the tab. In an embodiment, the tab includes one or more indicators. In an embodiment, the tab has an indicator 400 on one or more major surfaces. In an embodiment, the tab has an indicator 400 on one or more minor surfaces. In an embodiment, the tab has an indicator 400 on every surface. In an embodiment, the tab has an indicator 400 inside a material making up the tab. In an embodiment, the indicator 400 is removable from the tab. In an embodiment, the indicator 400 is attachable to the tab. In an embodiment, the indicator 400 is in the tab.
[0023] The indicator 400 may be visual or tactile or both. A visual indicator 400 includes letters, numbers, logos, icons, signs, barcode, any marking, or combinations thereof. A tactile indicator 401 includes textures to permit identification of a specific tag by the feel of the tab. Texturing can be provided by protrusions, indentations, alternate layers of material, additions of objects adhered to the tab, or combinations thereof, which allows an appropriate tactile feel. Tactile indicators allow identification in dark environments. For individuals who have impaired sight, the tactile indicator may include Brail encodings which would allow for identification and the user's selection of desired card.
[0024] Indicators may be used to provide advertisements and/or commercial advantages. For example, in certain commercial settings where it is desirable to provide coupons, discounts, or loyalty program content, the tab may include an indicator which may be encoded with a conventional barcode, such as a PDF417 or code 148, or similar indicator, which enables commercially available barcode scanners to read the coupon content or loyalty content thereby enabling a single card/loyalty enablement. For example, a grocery store that provides reward cards can provide a reward tab which when scanned as part of the checkout process provides rewards to the consumer. The consumer needs have only the card/tab combination to initiate both rewards and payments. An embodiment of the organization aid device 100 includes one or more of the indicators stated above.
[0025] An embodiment includes a card-like device connected to the organization aid device 100 . In an embodiment, the organization aid device 100 includes a tab portion 202 and a surface including an adhesive for adhering the surface to the card-like device. In an embodiment, an adhesive permits either permanent or temporary adhesion to the credit card 300 . In an embodiment, the organization aid device 100 includes an adhesive which permits a permanent adhesion to the credit card 300 . In an embodiment, the organization aid device 100 includes an adhesive which permits a temporary adhesion to the credit card 300 . In an embodiment, the organization aid device 100 has a surface including an indicator 400 and an adhesive thereon. In an embodiment, the organization aid device 100 has a first surface including an indicator 400 and a second surface including an adhesive thereon. In an embodiment, the organization aid device 100 has a first surface including an indicator 400 and a second surface including a second indicator 403 and an adhesive thereon.
[0026] An embodiment of the organization aid device 100 is made of a thin sheet of polycarbonate material. An embodiment of the organization aid device 100 includes a tab which is made of a thin sheet of polycarbonate material. An embodiment of the organization aid device 100 is made of a thin sheet of polycarbonate material on which is imprinted an indicator 400 . An embodiment of the organization aid device 100 includes a tab which is made of a thin sheet of polycarbonate material on which is imprinted an indicator 400 . An embodiment of the organization aid device 100 is made of a thin sheet of polycarbonate material on which is imprinted a logo corresponding to a brand of a credit card 300 . An embodiment of the organization aid device 100 includes a tab which is made of a thin sheet of polycarbonate material on which is imprinted a logo corresponding to a brand of a credit card 300 .
[0027] An embodiment of an organization aid device 100 consists of a thin sheet, an indicator 400 disposed on a surface of the thin sheet, and an adhesive on at least a portion of the thin sheet. An embodiment of an organization aid device 100 consists of a thin sheet, an RFID chip in the thin sheet, and an adhesive on at least a portion of the thin sheet. An embodiment of an organization aid device 100 consists of a thin sheet, an RFID chip in the thin sheet, an indicator 400 disposed on a surface of the thin sheet, and an adhesive on at least a portion of the thin sheet. As shown in FIGS. 1 a and lb, an embodiment of the organization aid carrier device 10 includes one or more organization aid devices 100 , 101 , 102 , 103 , 104 , 105 and a carrier portion 106 .
[0028] An embodiment of the organization aid carrier device 10 comprises a plurality of organization aid devices 100 , 101 , 102 , 103 , 104 , 105 configured to be detachable from a carrier portion 106 . In an embodiment, each of the organization aid devices 100 , 101 , 102 , 103 , 104 , 105 of the organization aid carrier device 10 includes a first surface having an indicia, and a second surface that includes an adhesive layer 200 between the second surface and a removable layer 201 . In an embodiment, the organization aid devices 100 , 101 , 102 , 103 , 104 , 105 are fabricated as a single piece with perforations between the organization aid devices 100 , 101 , 102 , 103 , 104 , 105 which permit individual organization aid devices 100 , 101 , 102 , 103 , 104 , 105 to be separated from the carrier portion 106 , as shown in FIG. 2 .
[0029] One embodiment of the organization aid carrier device 10 is made of a single material, having two major surfaces, wherein on a portion of one of the major surfaces is a layer of adhesive, a protective removable layer on top of the adhesive layer configured to be removable by a user, wherein an etched line, perforation, and/or scored line, is provided on one of the major surfaces such that one of the organization aid devices 100 , 101 , 102 , 103 , 104 , 105 may be separated from the carrier portion 106 of the organization aid carrier device 10 .
[0030] An embodiment of the organization aid carrier device 10 is sized to be a card-like device. Accordingly, the embodiment of the organization aid carrier device 10 follows one of the international standards that defines the physical characteristics, such as for example, ISO/IEC 7810, ISO/IEC 7813, ISO/IEC 7811, and/or ISO/IEC 7816. Accordingly, the embodiment of the organization aid carrier device 10 may have dimensions according to ID-1, ID-2, ID-3, or ID-000. One embodiment of the organization aid carrier device 10 has dimensions of 85.60 mm×53.98 mm. One embodiment of the organization aid carrier device 10 has dimensions of 105 mm×74 nun One embodiment of the organization aid carrier device 10 has dimensions of 125 mm×88 mm. One embodiment of the organization aid carrier device 10 has dimensions of 25 mm×15 mm.
[0031] One embodiment of the organization aid carrier device 10 follows ISO/IEC 7813 and has dimensions of 85.60 mm×53.98 mm, a thickness of 0.76 mm, and corners rounded with a radius of 3.18 mm.
[0032] In an embodiment, the carrier portion 106 includes an advertising display. In an embodiment, the organization aid carrier device 10 includes six organization aid devices 100 , 101 , 102 , 103 , 104 , 105 , each configured to be detachable. In an embodiment, the organization aid carrier device 10 is substantially the same size as the credit card 300 . In an embodiment, the organization aid carrier device 10 is substantially the same size as the card-like device. In an embodiment, the organization aid carrier device 10 includes an extension of material outside of the organization aid device 100 for retail display. In an embodiment, the organization aid carrier device 10 includes a “j hook” connected to the carrier portion 106 for retail display. The carrier portion 106 may include instructions on the method of using the carrier aid device.
[0033] An embodiment of a system for organizing card-like devices includes a stack of card-like devices in a single pouch, such as for example, but not limited to, in a wallet. The embodiment of the system includes one or more cards having an attached tab. In an embodiment of the system including at least two cards each having an attached tab, the tabs are in staggered position relative to each other for easy identification, permitting grasping of one tab isolated from the other tab(s) and separating the desired card attached to the grasped tab from the stack. The staggered tabs may overlap. The staggered tabs may not overlap.
[0034] An embodiment of a system for organizing card-like devices includes a stack of card-like devices, wherein each of the card-like devices includes an organization aid device 100 attached to a surface of the card-like device, wherein the organization aid device 100 includes a tab portion 202 that extends away from an edge of the card-like device.
[0035] Use of the organization aid devices 100 , 101 , 102 , 103 , 104 , 105 as a system can be for single cards or groups of cards. In group usage, the organization aid devices 100 , 101 , 102 , 103 , 104 , 105 can be offset by a distance, for example, a distance equal to the width of the tab, thus permitting visual and/or tactile identification of, for example, which credit card 300 or card-like device is attached to the particular tab or a portion of the organization aid device 100 that can be identified. The orientation of the organization aid device 100 attached to the card-like device 300 can be either perpendicular to the long side or the short side of the card 300 . In other words, the orientation of the attachment of the organization aid device 100 , 101 to the card-like device 300 can be near an edge of the length side or the width side, as shown in FIG. 4 , which shows examples of both attachment orientations on one card-like device 300 . User selection of orientation permits a variety of wallet structures from which card-like devices can be accessed, stored, and/or removed based on the desire and convenience of the user.
[0036] The organization aid devices 100 , 101 , 102 , 103 , 104 , 105 may be removable as necessitated by the use with an ATM type device that is configured to ingest the entire card-like device for reading. Alternatively, tabs can be fabricated by an extremely flexible albeit strong material, such as 1 mil Mylar, or 2 mil Mylar, and/or other thin shaped flexible material, which can readily survive the ingestion without damage or jamming the reader mechanism.
[0037] The fabrication technologies of the organization aid device 100 and/or the organization aid carrier device 10 can be performed by multi-laminate printing technologies on a variety of material stocks. In a preferred embodiment, the organization aid device 100 and/or the organization aid carrier device 10 is produced as sections of a single conventional 18×24 printer sheet through a multi-pass lamination process in which various layers, substrate, adhesive, overprint layers (top & bottom) are laminated onto the sheet producing a multiple of card templates. A final press run through a die cutter separates the cards from the sheets and also segments the tabs for mechanical removal by the consumer. The process is a printing process which can be performed by conventional printing means, thereby dramatically reducing the costs of production.
[0038] In an embodiment, the organization aid device 100 and/or the organization aid carrier device 10 can be fabricated in a manner which includes the incorporation of a smart chip, an RFID tag, and/or an RFID chip. Incorporating the smart chip, the RFID tag, and/or the RFID chip into the organization aid device 100 makes the organization aid device 100 a “smart tab.” The smart tab can be used to enhance the information content of the card-like device and give the card-like device the functional equivalence of a smart card at a fraction of the cost of a typical smart card. Additionally, this avoids the mechanical design aspects of a smart card which limit the life expectance due to flex breakage. In an embodiment, the card-like device retains functionality of the original card-like device and only the organization aid device 100 need to be replaced with a new and/or different embedded electronics module or chip. Further, tiered capabilities for a given card can be granted by a selection of appropriate “smart tabs”. For example, tier one may be a smart chip organization aid device 100 with a few kilobytes of data storage whereas an advance tier may contain a smart chip organization aid device 100 with a few megabytes of data storage. Other variations to those described herein are also envisioned.
[0039] Adhesives used on the organization aid device 100 can be either strong or removable. By choosing from a variety of tack properties for pressure sensitive adhesives, for example any of the pressure sensitive styrene block copolymer family commercially available from many companies such as 3M, the degree of adhesion between the tab and card can be permanent, or removable, or reusable, depending on the intended use of the card.
[0040] A preferred embodiment has been described for illustrative purposes. Those skilled in the art will appreciate that various modifications and substitutions are possible without departing from the scope of the invention, including the full scope of equivalents thereof. | An organization aid device, an organization aid carrier device, system, and method for organizing and retrieving cards is disclosed. The organization aid device allows for organization of plurality of card-like devices and quick identification of a particular card-like device from a stack of similar card-like devices, such that when a plurality of card-like devices are stored in a confined carrier, a desired card-like device can be accurately retrieved from the rest of the card-like devices and/or from the confined carrier. | 1 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a washing machine, and more particularly to a pulsator assembly for a washing machine.
2. Description of the Prior Art
Generally, a washing machine washes a laundry article according to predetermined washing cycles. That is, general washing cycles are composed of a water supply step, a washing step, a rinsing step, a draining step and a dehydrating step. During the water supply step, water is supplied to a water reservoir of the washing machine, the washing step is introduced to wash the laundry article, the washed laundry article is rinsed at the rinsing step, the used water is drained from the water reservoir at the draining step, and finally at the dehydrating step water soaked in the laundry article is removed therefrom. As shown in FIG. 1, the conventional washing machine has a water reservoir 5, which is mounted within a retangular box-shaped main body, for containing water. Within water reservoir 5, a washing tub 4 in which laundry articles are put is provided. A pulsator 6 is rotatably installed at the inner bottom of washing tub 4. Pulsator 6 agitates the water in washing tub 4. The middle of pulsator 6 is fixed at one end of a shaft 2 by a bolt 3. Shaft 2 passes through the center of washing tub 4 and water reservoir 5. At the other end of shaft 2 a shaft pulley 7 is fixed. Shaft 2 is rotatably mounted by a shaft housing 8 disposed at the center of the outer bottom of water reservoir 5 as shown in FIG. 1A. At the outer bottom of water reservoir 5, a driving motor 1 is provided. At the shaft of driving motor 1, a driving pulley 9 is connected. Driving pulley 9 and shaft pulley 7 are connected to each other by means of a pulley belt 15. Accordingly, forward or reverse driving power generated when driving motor 1 rotates in a forward or reverse direction is transmitted to shaft 2 through pulley belt 15 and rotates shaft 2 forwards or in reverse. Such rotations of shaft 2 cause pulsator 6 to be rotated. By the rotation of pulsator 6 the laundry article contained in washing tub 4 is cleaned.
However, in the conventional pulsator assembly as mentioned above, when a laundry article in washing tub 4 is being washed, pulsator 6 experiences heavy load caused by the laundry article since pulsator 6 is fixed to one end of shaft 2. Thus, if pulsator 6 operates with a heavy load for a long time period, pulsator 6 likely accumulates fatigue to decrease a strength of pulsator 6, thereby causing pulsator 6 to be finally damaged. Also, in such conventional pulsator assembly as mentioned above, since pulsator 6 is disposed in parallel with the bottom of washing tub 4, it is difficult to increase the washing power by vortex water current as well as to prevent laundry articles from being twisted and tangled.
SUMMARY OF THE INVENTION
It is the object of the present invention to provide a pulsator assembly for a washing machine capable of increasing a washing efficiency by causing a vortex water current and preventing laundry articles from being tangled and twisted.
To achieve the above object, a pulsator assembly for a washing machine according to the present invention comprises a shaft pulley, a shaft, a connecting member, a confining part, an engaging part and a pulsator. The shaft pulley is connected to a driving pulley of a driving motor by means of a pulley belt. Accordingly, driving force for a forward or reverse rotation which is generated when the driving motor is rotated forwards or in reverse is transmitted to the shaft pulley through the pulley belt. One end of the shaft is fixed to the shaft pulley. The shaft rotates forwards or in reverse depending on the forward or reverse driving force transmitted to the shaft pulley. The other end of the shaft is engaged with the lower end of the connecting member. At the upper center of the connecting member, an inserting hole is formed due to engagement with the shaft. Along the outer periphery of the connecting member a plurality of fixed projecting portions are formed with a certain distance therebetween. The connecting member rotates forwards or in reverse according to the forward or reverse rotation of the shaft. A plurality of fixed projecting portions are engaged with the pulsator. The pulsator includes a plurality of grooves on the lower surface of the pulsator to receive the projecting portions of the connecting member as well as has a protuberance portion at the center of the lower surface thereof, and a sphere-shaped ball portion is provided at the end of the protuberance portion. The pulsator rocks in right, left, up and down directions while rotating forwards or in reverse according to the forward or reverse rotation of the connecting member. The plurality of fixed projecting portions of the connecting member are inserted into the plurality of grooves of the pulsator in a one to one manner and the ball portion of the pulsator is inserted into the inserting hole of the connecting member. The size of a groove is larger than that of a fixed projecting portion so that the pulsator can freely move without being fixed by the fixed projecting portions. The diameter of the inserting hole is larger than that of the ball portion in order for the ball portion to be freely rotated inside the inserting hole. Also, the pulsator assembly according to the present invention includes the confining part. The confining part is provided between the pulsator and the connecting member in order for the ball portion of the pulsator not to separate from the inserting hole of the connecting member. The engaging part fixes the confining part to the connecting member.
At a washing step, the rotation of the pulsator causes water and laundry article contained in a washing tub to be agitated. By this agitation of the water and laundry articles, the pulsator becomes loaded. At this time, as a load on the pulsator varies due to a change of a rotating speed or direction of the pulsator as well as due to the laundry article striking with the pulsator, the pulsator moves in right, left, up and down directions while rotating. This, as stated in the foregoing, is possible because the grooves of the pulsator and the fixed projecting portions of the connecting member are freely engaged with each other and the ball portion of the pulsator is inserted into the inserting hole of the connecting member so as to be freely rotatable by means of the confining part. Such irregular movements of the pulsator prevents the pulsator from being damaged by an overload to the pulsator due to the weight of laundry articles. Additionally, the rocking of the pulsator generates a vortex current of laundry water, and accordingly, the washing efficiency is increased and the tangling among the laundry articles is reduced.
BRIEF DESCRIPTION OF THE DRAWINGS
The above object and other features of the present invention will become apparent by describing a preferred embodiment of the present invention with reference to the accompanying drawings in which:
FIG. 1 is a brief schematic sectional view of a washing machine for showing a pulsator assembly installed in a conventional washing machine;
FIG. 1A is a sectional extending view for showing the engagement state of the shaft and pulsator depicted in FIG. 1.
FIG. 2 is an exploded perspective view of a pulsator assembly for a washing machine according to an embodiment of the present invention;
FIG. 3 is a sectional view of a connecting member shown in FIG. 2;
FIG. 4 is a sectional view of a shaft shown in FIG. 2; and
FIG. 5 is a sectional view of the pulsator assembly for a washing machine shown in FIG. 2.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
Hereinafter, a pulsator assembly for a washing machine according to a preferred embodiment of the present invention is described referring to the attached drawings.
FIG. 1 is a brief schematic sectional view of a washing machine for showing a pulsator assembly installed in a conventional washing machine, and FIG. 2 is an exploded perspective view of a pulsator assembly according to an embodiment of the present invention. In describing the pulsator assembly according to the embodiment of the present invention, reference numerals as shown in FIG. 1 are used for indicating general constitutional members of a washing machine. As shown in the drawings, a pulsator assembly for a washing machine according to the embodiment of the present invention comprises a shaft pulley 13, a shaft 10, a connecting member 30, a confining part 39, a engaging part 50 and a pulsator 20. Shaft pulley 13 is connected to a driving pulley 9 of a driving motor 1 by means of a pulley belt 15. Accordingly, driving force for a forward or reverse rotation which is generated when driving motor 1 is rotated forwards or in reverse is transmitted to shaft pulley 13 through pulley belt 15. One end of shaft 10 is fixed to shaft pulley 13. Shaft 10 rotates forwards or in reverse depending on the forward or reverse driving force transmitted to shaft pulley 13. The other end of shaft 10 is engaged with the lower end of connecting member 30. At the upper center of connecting member 30, an inserting hole 32a is formed due to engagement with shaft 10. Along the outer periphery of connecting member 30 a plurality of fixed projecting portions, for example, four fixed projecting portions 31 are provided at a certain distance therebetween. Connecting member 30 rotates forwards or in reverse according to the forward or reverse rotation of shaft 10. A plurality of fixed projecting portions are engaged with pulsator 20. The upper portion of connecting member 30 is engaged with pulsator 20. Pulsator 20 includes a plurality of grooves, for example, four grooves 23, on the lower surface of pulsator 20, a protuberance portion 20b is formed on the center of the lower surface thereof, and a sphere-shaped ball portion 24 is formed on the lower end of protuberance portion 20b. Pulsator 20 rocks in right, left, up and down directions while rotating forwards or in reverse according to the forward or reverse rotation of connecting member 30. A plurality of fixed projecting portions 31 of connecting member 30 are inserted into a plurality of grooves 23 of pulsator 20 in a one to one manner and ball portion 24 of pulsator 20 is inserted into inserting hole 32a of connecting member 30. The size of a groove 23 is larger than that of fixed projecting portion 31 so that pulsator 20 can freely move without being fixed to fixed projecting portion 31. The diameter of inserting hole 32a is larger than that of ball portion 24 in order for ball portion 24 to be freely rotated inside inserting hole 32a. Further, the pulsator assembly according to the embodiment of the present invention includes confining part 39. Confining part 39 is provided between pulsator 20 and connecting member 30 in order for ball portion 24 of pulsator 20 not to separate from inserting hole 32a of connecting member 30. Engaging part 50 fixes confining part 39 at connecting member 30. FIG. 4 is a sectional view of the shaft of FIG. 2. As shown in FIGS. 2 and 4, shaft 10 includes a shaft body portion 10a, a first cylinder portion 10b and a second cylinder portion 10c. Shaft body portion 10a is cylinder-shaped and one end thereof is fixed to shaft pulley 13. On the other end of shaft body portion 10a, first cylinder portion 10b is formed. First cylinder portion 10b is in the shape of a cylinder with a little smaller diameter than that of shaft body portion 10a. On the outer periphery surface of first cylinder portion 10b a screw thread 12 is formed. On first cylinder portion 10b second cylinder portion 10c is placed. Second cylinder portion 10c is also formed in a cylinder with smaller diameter than that of first cylinder portion 10b. On the upper surface of second cylinder portion 10c, an arc-shaped recess 11 is formed. FIG. 3 is a sectional view of the connecting member of FIG. 2. As shown in FIGS. 2 and 3, connecting member 30 includes a connecting member body portion 30a and fixed projecting portion 31. Connecting member body portion 30a has the same size of diameter as that of shaft 10, and a through hole 30b is formed at the center of connecting member body portion 30a. On the upper end of connecting member body portion 30a, a plurality of fixed projecting portions 31 are provided along the outer periphery of connecting member body portion 30a with a certain distance therebetween. Through hole 30b has a female screw portion 30d, a ball-receiving hole portion 30f and a communicating hole portion 30e. A screw thread is formed along the inner periphery surface of female screw portion 30d. The diameter of female screw portion 30d is the same as that of first cylinder portion 10b. Ball-receiving hole portion 30f has a ball-shaped space portion for receiving the ball portion. Communicating hole portion 30e allows female screw portion 30d and ball-receiving hole portion 30f to be communicated. The diameter of communicating hole portion 30e is the same as that of second cylinder portion 10c. Also, connecting member body portion 30a further includes a first engaging hole 51a and a second engaging hole 51b. First and second engaging holes 51a and 51b are disposed respectively in parallel with communicating hole portion 30e and pass through from female screw portion 30d to the upper end of connecting member 30 respectively. On each of the inner periphery surfaces of first and second engaging holes 51a and 51b, a screw thread is formed. FIG. 5 is a sectional view of the pulsator assembly for a washing machine of FIG. 2. As shown in FIGS. 2 and 5, pulsator 20 includes a disc-shaped pulsator body portion 20a, a protuberance portion 20b and a ball portion 24. Pulsator body portion 20a includes a round base plate 22 and a wing piece 21 of a predetermined shape. Wing piece 21 is disposed on round base plate 22. On the lower surface of round base plate 22 a plurality of grooves 23 are formed with a certain distance therebetween. On the center of the lower surface of round base plate 22, protuberance portion 20b is formed. On the lower end of protuberance portion 20b sphere-shaped ball portion 24 is formed. The predetermined shape of wing piece 21 may be a wave form and the wing piece is integrally formed with round base plate 22. Confining part 39 includes a first confining piece 40 and a second confining piece 40'. First confining piece 40 has a first engaging hole 41 and a first confining recess 42 and second confining piece 40' has a second engaging hole 41' and a second confining recess 42' First confining piece 40 and second confining piece 40' are respectively disposed inside a plurality of fixed projecting portions 31. First confining recess 42 of first confining piece 40 and second confining recess 42' of second confining piece 40' are opposedly disposed to form a confining hole. The confining hole receives projecting portion 20b of pulsator 20 and prevents pulsator 20 from separating from connecting member 30. Each of first confining piece 40 and second confining piece 40' has the shape of a semicircle. Engagement part 50 includes a first bolt 50a and a second bolt 50b. First bolt 50a and second bolt 50b pass through first engaging through hole 51a and second engaging through hole 51b respectively and are engaged with first engaging hole 41 and second engaging hole 41' of first confining piece 40 and second confining piece 40' respectively. By doing so, first confining piece 40 and second confining piece 40' are fixed to connecting member 30.
In the pulsator assembly for a washing machine according to the embodiment of the present invention as shown in FIG. 1, pulsator 20 is rotatably installed at the inner bottom of washing tub 4 placed within water reservoir 5. Connecting member 30 engaged with pulsator 20 and shaft 10 is installed outside water reservoir 5, passing through the center portions of water reservoir 5 and washing tub 4. Shaft 10 can be installed by shaft housing 8 to be rotated, and shaft housing 8 is situated at the center of the outer bottom of water reservoir 5. Shaft pulley 13 engaged with one end of shaft 10 is connected to driving pulley 9 of driving motor 1 by means of pulley belt 15.
The pulsator assembly for a washing machine with such a construction as above according to the embodiment of the present invention operates in the following manner.
Water is supplied into water reservoir 5 of a washing machine. Washing tub 4 is provided in water reservoir 5. A laundry article is put into washing tub 4. When driving motor 1 works at the washing step, a rotating force of driving motor 1 is transmitted to shaft pulley 13 by way of pulley belt 15 and driving pulley 9 to thereby rotate shaft pulley 13. Shaft pulley 13 rotates in a forward or reverse direction according to the rotating direction of driving motor 1. The rotation of shaft pulley 13 causes shaft 10, connecting member 30 and pulsator 20 to be rotated. The rotation of pulsator 20 agitates the water and laundry articles. By this agitating of the water and laundry articles, pulsator 20 becomes loaded. At this time, as the load carried by pulsator 20 varies due to a change of a rotating speed or direction of pulsator 20 or due to the laundry article striking with pulsator 20, pulsator 20 moves in right, left, up and down directions while rotating. This, as stated in the foregoing, is possible because grooves 23 of pulsator 20 and fixed projecting portions 31 of connecting member 30 are movably engaged with each other and ball portion 24 of pulsator 20 is rotatably engaged with inserting hole 32a of connecting member 30 by means of confining part 39. Such irregular movements of pulsator 20 prevent pulsator 20 from being overloaded due to the weight of laundry articles. Additionally, the rocking of pulsator 20 generates a vortex water current of laundry water, and accordingly, a washing efficiency is increased and tangling of the laundry articles is reduced.
Although the pulsator assembly for a washing machine has been described through a preferred embodiment of the present invention, variations and changes may be made without departing from the scope and the spirit of the invention. | Disclosed is a pulsator assembly for a washing machine. The pulsator assembly comprises a pulsator rocking in right, left, up and down directions while rotating forwards or in reverse according to a forward or revere rotation force and a connecting member engaging the pulsator with a shaft while freely moving the pulsator. The free rocking movements of the pulsator prevent the pulsator from being damaged due to a overload of laundry articles and create a vortex water current to increase a cleaning efficiency as well as to decrease the tangling of the laundry articles. | 3 |
Acknowledgement
Part of the invention was made under financial support of the National Institute of Health.
This is a division of application Ser. No. 181,833, filed Aug. 27, 1980.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates to a method and reagent for the opening of the cyclopropyl ring of vinyl cyclopropyl compounds with the simultaneous introduction of a nucleophile into the product compound. More particularly, the present invention relates to a method of converting unsaturated fatty acids containing a vinyl cyclopropyl structure to a hydroxy or hydroperoxy fatty acid.
2. Description of the Prior Art
Both the hydroxy and hydroperoxy derivatives of certain fatty acids conventionally formed by the action of lipoxygenase enzymes on various acid substrates are of medical interest because it is believed that they play significant roles in platelet pharmacology and in the inflammation of various tissues. For example, 12-L-hydroxy-5,8,10,14-eicosatetraenoic acid exhibits chemotatic activity on neutrophils. The corresponding hydroperoxy derivative as well as other hydroperoxy positional isomers modulate the enzymes that control prostaglandin metabolism. E. J. Corey et al, J. Am. Chem. Soc., 100, 1942 (1978) recently have described a total synthesis of this compound.
Recently, two previously unknown monohydroxy C 20 fatty acids, 5-L-hydroxy-6,8,11,14-eicosatetraenoic acid, whose chemical and enzymatic synthesis has recently been reported by E. J. Corey et al J. Am. Chem. Soc., 102, 1435 (1980), and 8-L-hydroxy-9,11,14-eicosatetraenoic acid, have been isolated from rabbit neutrophils. The structure of these compounds which contains a cis, trans conjugated diene unit suggests that the mono-hydroxy acid compounds are probably formed from the corresponding intermediate hydroperoxy compounds. In fact, it has been demonstrated that the hydroxy group of 5-L-hydroxy-6,8,11,14-eicosatetraenoic acid is derived from molecular oxygen which is a finding consistent with the intermediacy of the corresponding hydroperoxy compound.
Interest in all of the above-discussed compounds as well as their hydroperoxy intermediates has also been heightened by the postulate that 5-L-hydroperoxy-6,8,11,14-eicosatetraenoic acid is a key intermediate in the biosynthesis of leukotrienes. One member of this important group of compounds is leukotriene C, which is the slow reacting substance of anaphylaxis, which causes prolonged smooth muscle contraction that is not inhibited by conventional anti-histamines. Leukotriene C is also believed to be intimately involved in the allergic response and may very well be an important factor in certain types of asthma. Samuelsson et al (Proc. Nat. Acad. Sci, 76, 4275 (1979)) has suggested that leukotriene C is biochemically prepared by a series of reactions in which 5-L-hydroperoxy-6,8,11,14- eicosatetraenoic acid (an arachidonic acid hydroperoxide) is converted to leukotriene A, which is an epoxide. Leukotriene A is then converted to leukotriene C by reaction with the cysteine sulfur nucleophile. Even though the above suggested synthetic scheme has not been unequivocally established, nevertheless the fundamentally important function which the arachidonic acid hydroperoxide derivatives exhibit in inflammation and in certain forms of asthma is gaining increased recognition by the scientific community.
In view of the above developments there is an obvious need for a study of the oxidative metabolism of unsaturated fatty acid compounds. The oxidation products (endoperoxides and hydroperoxides) are evidently important factors in such major traumatic events as the inflammation process, blood platelet aggregation and consequently heart attack and stroke and the allergic response. Studies, therefore, directed to an understanding of the fundamental chemistry involved in fatty acid oxidation are believed to be important to a proper understanding of these pathological conditions. Previous attempts at synthesizing various hydroxy and hydroperoxy derivatives of various unsaturated compounds have been limited to enzyme catalyzed oxidation reactions of unsaturated fatty acids and such non-enzymatic reactions as the reaction of singlet oxygen generated by photolysis of molecular oxygen with the likes of arachidonic acid. (Porter et al, J. Org. Chem., 44, 3177 (1979)). Another proposed method of synthesis involves the autooxidation of arachidonic acid. However, in both known non-enzymatic oxidation reactions, a complex mixture of product compounds is obtained in low yield which requires tedious chromatographic separation. A need, therefore, continues to exist for a method by which unsaturated fatty acid substrates can be oxidized to just a few, rather than a broad spectrum of possible corresponding hydroperoxy and hydroxy derivatives in good yield.
SUMMARY OF THE INVENTION
Accordingly, one objective of the present invention is to provide a method by which unsaturated fatty acid compounds can be oxidatively converted by a nonenzymatic process to a selectively narrow spectrum of hydroperoxy and hydroxy derivatives in good yield.
Another object of the present invention is to provide a method by which hydroperoxy functionality can be introduced into an unsaturated hydrocarbon compound. Yet another object of the invention is to provide hydroperoxy and peroxy derivatives of unsaturated fatty acid compounds for a study of the role of these derivatives in several pathological conditions relating to the allergic response, inflammation and blood platelet aggregation.
Briefly, these objects and other objects of the present invention as hereinafter will become more readily apparent can be attained by a method for synthesizing a nucleophile substituted unsaturated hydrocarbon based compound by reacting a compound of the formula: ##STR2## wherein R and R' independently are hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, alkoxyalkyl, alkoxy, alkylthioalkyl, carboxyalkyl, or carboxyalkenyl, and X is a leaving group selected from the group consisting of chlorine, bromine and iodine, with a nucleophilic reagent.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
The central feature of the present invention is based upon the discovery that when a vinyl cyclopropyl compound bearing an appropriate leaving substituent is reacted with a nucleophile, the cyclopropyl ring is opened with the attachment of the nucleophile to a portion of the molecule. When the cyclopropyl ring is opened, a new olefinic bond is formed within the molecule which is conjugate to the olefinic bond of the vinyl group or an olefinic bond derived from the vinyl group. The key feature of the reactive vinylcyclopropyl substrate of the present invention is the attachment of a vinyl group on the cyclopropyl ring and the presence of a leaving group at one of the other two carbon atoms of the cyclopropyl ring.
The vinyl cyclopropyl compound employed in the present invention has the formula: ##STR3## wherein substituents R and R' are hydrogen, alkyl of four to ten carbon atoms, alkenyl of four to ten carbon atoms containing at least one site of unsaturation, cycloalkyl, cycloalkenyl, aryl, aralkyl, alkoxyalkyl, alkoxy, alkylthioalkyl, carboxyalkyl, carboxyalkenyl, or the like.
Suitable specific examples of substituents include methyl, ethyl, propyl, butyl, hexyl, vinyl, propenyl, butenyl, hexenyl, cyclopentyl, cyclohexyl, cyclohexenyl, phenyl, naphthyl, benzyl, phenethyl and the like.
Suitable leaving substituents (X) include bromo, chloro, iodo, and the like.
The nucleophile which reacts with the vinylcyclopropyl substrate can be any nucleophile which will attack the cyclopropyl ring of the substrate or the vinyl group or an olefinic group conjugate to the vinyl group and bond to the site which it attacks and causes the opening of the cyclopropyl ring with the elimination of the leaving group (X) and formation of an olefinic bond in conjugation with the olefinic bond of the vinyl group or olefinic group derived from the vinyl group. Suitable nucleophilic agents which can react with the vinylcyclopropyl compound include amines, organosulfides, organohydroperoxides, alkoxides, and the like. An especially preferred nucleophile is a Ag + salt/H 2 O 2 mixture which permits the introduction of a hydroperoxy substituent in the product compound. Suitable silver salts include the likes of silver nitrate, silver sulfate, silver trifluoroacetate, and the like.
The cyclopropyl ring opening reaction can be simply conducted by reacting the vinylcyclopropyl compound with the nucleophilic reagent under nonstrenuous conditions. Thus, the reaction can be conducted at temperatures ranging from 0° to 40° C. in a solvent which dissolves the vinylcyclopropyl compound and facilitates the reaction of the nucleophilic reagent with the vinylcyclopropyl compound. Suitable solvents include dialkyl ether compounds such as diethylether, dipropylether; dialkylformamide compounds such as dimethylformamide; acetonitrile; trifluoroethanol; dimethylsulfoxide and the like. The amounts of vinylcyclopropyl compound and nucleophilic reagent employed in the reaction are not critical with the only objective being to conduct the reaction as far as possible to completion. Accordingly, the amount of nucleophilic reagent reacted with the vinylcyclopropyl compound can range from one to one hundred moles of nucleophilic reagent per mole of vinylcyclopropyl compound.
In a preferred embodiment of the present invention a fatty acid derivative containing a vinyl cyclopropyl structure of the formula: ##STR4## is reacted with a nucleophilic reagent. A preferred nucleophilic reagent in the reaction is Ag + salt/H 2 O 2 mixture which introduces a hydroperoxy substituent in the product. Accordingly, the use of this particular nucleophilic reagent permits the synthesis of an important group of hydroperoxy and hydroxy substituted unsaturated fatty acids or esters thereof which are found in biological systems. The hydroperoxy group can also be introduced into the product molecule by using an organohydroperoxide of the formula ROOH, wherein R is an alkyl or aryl radical, in place of hydrogen peroxide in the above mentioned nucleophilic reagent. The product of the reaction will contain an organoperoxy group from which the R radical can be removed and replaced by hydrogen by conventional reaction methodology.
In the above formula of the unsaturated acid or ester derivative, suitable R" substituents include hydrogen; alkyl such as methyl, ethyl, pentyl, hexyl and the like; alkenyl containing at least one olefinic site such as vinyl, propenyl, butenyl, hexenyl, heptenyl, CH 3 (CH 2 ) 4 --CH═CH--, CH 3 (CH 2 ) 4 CH═CH--CH 2 --CH═CH--, and the like, aralkyl and aralkenyl containing at least one olefinic site such as phenylvinyl, phenylpropenyl and the like. Suitable L substituents include alkylene of three to nine carbon atoms; alkylene of three to nine carbon atoms containing at least one olefinic group such as --CH 2 CH═CHCH 2 CH═CH(CH 2 ) 3 --, --CH 2 CH═CH--(CH 2 ) 3 --, and the like. Suitable R'" substituents include hydrogen and alkyl such as methyl, ethyl, butyl, pentyl, and the like; aryl; aralkyl; and the like. The leaving group X is the same as defined above.
Another embodiment of the vinylcyclopropyl group containing fatty acid or ester compounds of the present invention includes compounds of the formula: ##STR5## wherein R", R'", L and X are as defined above.
In addition to the nucleophilic reagent described above for the introduction of the hydroperoxy substituent in the fatty acid molecule, other nucleophilic reagents can be used as described earlier depending upon the typoe of substituted fatty acid product desired. The conditions employed for the synthesis of the hydroperoxy or hydroxy substituted fatty acid product are the same as those described above.
If it is desired to reduce the hydroperoxy group in the product fatty acid or ester molecule to the corresponding hydroxy group, this can be done with the use of an appropriate reducing agent by conventional reaction methodology. Suitable reducing agents include triarylphosphines such as triphenylphosphine trialkylphosphites, mercaptans, organosulfides and the like.
The utility of the method of the present invention is that it provides a relatively simple way of synthesizing compounds which have been shown or are suspected to possess significant biological properties relating to inflammation, the allergic response and blood platelet aggregation. The present invention also provides a general synthetic technique by which a cyclopropyl ring within a molecule can be opened to introduce another olefinic bond into the molecule while also introducing a substituent in the molecule.
Having generally described the invention, a further understanding can be obtained by reference to certain specific examples which are provided herein for purpose of illustration only and are not intended to be limiting unless otherwise specified.
EXAMPLE 1
2-Hydroperoxy-3, 5-heptadiene
To a 5 ml round bottom flask are added 4 mg (.023 mmoles) 2-bromo-3-(1-propenyl) methylcyclopropane, 270 μl 1 anhydrous ether and 270 μl 90% HOOH (450 equivalents). In one addition, 510 mg silver trifluoroacetate (100 equivalents) are added and the solution is stirred at room temperature for 15 minutes. The reaction is diluted with 15 ml ether, washed once with 10 ml saturated NaHCO 3 , and once with 10 ml saturated NaCl solution, then dried over MgSO 4 . After filtration, the product hydroperoxides are either converted to their corresponding alcohols or are concentrated on a rotovaporator and purified by chromatography (Water's μ porasil, 15% EtoAc/hexane). ##STR6## The hydroperoxides obtained were reduced to the corresponding hydroxy compounds as follows:
2-Hydroxy-3,5-heptadiene
To a 25 ml round bottom flask is added the crude 15 ml ether solution containing the product hydroperoxides. A few drops of water are added to `wet` the ether followed by approximately 100 mg triphenyl phosphine. The solution is stirred at room temperature for 15 minutes then dried over MgSO 4 . After filtration, the solution is concentrated to approximately 1 ml for capillary GC analysis. The hydroxy products obtained compared favorably with authentic samples of the alcohol products.
The following reactions were conducted in the manner described above and show the types of products obtained as a function of the structure of the vinyl cyclopropyl bromide compound used. ##STR7##
EXAMPLE 2
The following is the series of reactions employed to prepare the hydroperoxy compounds shown below. ##STR8##
Synthesis of Compound (B)
A mixture containing 32.4 gm (0.253 mol) of compound A 128 gm (0.506 mol) CHBr 3 in a solvent system containing 56 ml CH 2 Cl 2 , 90 ml 50% NaOH and 10 ml tetrabutylammonium hydroxide was stirred at 42° C. After 20 hr the reaction was stopped and the entire reaction contents were extracted with petroleum ether for 24 hr in a liquid-liquid continuous extractor. The petroleum ether solution was then washed several times with NH 4 Cl solution and with water. The organic solution was dried (MgSO 4 ) and then the solvent removed. The excess CHBr 3 was separated from the product by distillation (40°-50°/0.1 mm) leaving a yellow oil weighing 40 gm (52%). The product could be further purified by column chromatography on Florisil, eluting with 2% Et 2 O/98% C 6 H 14 . The dibromide (B) was thermally unstable and could not be distilled.
Synthesis of alcohol C
A solution containing 0.5 gm (2.0 mmol) dibromide (B) 2.0 gm (19.2 mmol) 2,2-dimethylpropandiol and a catalytic amount of toluenesulfonic acid in 9 ml of benzene was refluxed under a N 2 atmosphere. After four hr no starting material remained and the reaction was diluted with 25 ml benzene, washed with saturated NaHCO 3 solution and then three times with water and finally dried (MgSO 4 ). The products were purified via column chromatography on Florisil, eluting with 15% Et 2 O/85% C 6 H 14 . C(398 mg, 55%) was the most polar product.
Oxidation of compound C to the aldehyde
2.28 gm (6.37 mmol) (C) was oxidized with pyridinium chlorochromate at 15° C. The reaction progress was monitored by TLC. After ten hr reaction time all of (C) had been consumed. The crude product, an oil weighing 1.72 gm (75%), crystallized from Et 2 O. The colorless solid (85° dec.) slowly decomposes at room temperature.
Synthesis of acetal D
n-Hexyl-triphenylphosphonium bromide, 7.26 gm (17 mmol), was suspended in 52 ml of freshly distilled THF under a N 2 atmosphere at -20° C. To this was added dropwise 7.0 ml of a 2.4M (16.8 mmol) solution of n-butyllithium. The resulting orange colored ylid was stirred at -20° C. for 20 min, then the temperature was raised to 0°-5° C. To this ylid solution was added dropwise 1.52 gm (4.25 mmol) aldehyde dissolved in 8.5 ml dry THF. The resulting solution was then stirred for 2.25 hr at 0°-5° C. and then quenched by the addition of 8 ml cold H 2 O. The reaction mixture was diluted with Et 2 O and washed with brine and then water. The organic solution was dried (MgSO 4 ). The solvent was removed leaving an oil which was purified via cold column chromatography (-10° C.) on Florisil and 1% Et 2 O/99% C 6 H 14 eluant. The product D weighed 1.29 gm (71%).
Reaction of Compound D with methyl lithium
1.29 gm (3.04 mmole) D in 30 ml ether was cooled to -78° C. and to this solution was added 8 mmol methyllithium-lithium bromide over 4 min. The mixture was stirred for 20 min and quenched by the slow addition of 1 ml of water. The monobromide acetal was purified by cold column chromatography (-10° C.) eluting with 1% ether, 99% hexane. Yield: 0.836 gm (80%).
Synthesis of Compound E
A solution containing 96 mg (0.28 mmol) monobromide acetal in 0.5 ml THF and 3.5 ml of 88% formic acid were stirred at 0° under a N 2 atmosphere for 31 hr. At this time, all of the monobromide acetal was consumed. A mix of cold brine and ether was added to the reaction. The organic layer was washed three times with brine and then neutralized with saturated bicarbonate solution. The organic solution was dried (MgSO 4 ) and kept cold. Purification via cold column chromatography (-10° C.) on Florisil with 4% Et 2 O/96% C 6 H 14 eluent yielded 64 mg (88%) aldehyde (E). The aldehyde slowly decomposes at room temperature and should be stored at -20° C.
Synthesis of Wittig Product F
The phosphonium salt 0.370 gm (0.74 mmol) that was previously dried at 100° C./0.1 mm was dissolved in 3.5 ml of freshly distilled THF at room temperature and under a N 2 atmosphere. To this was added dropwise 1.4 ml (0.70 mmol) of 0.5M THF solution of potassium t-butoxide. The resulting ylid solution was stirred at room temperature for 15 min and then the temperature was lowered to 0°. A solution containing 1.6 ml dry THF and 63 mg (0.24 mmol) aldehyde was added dropwise. The resulting solution was stirred at 0° for three hr. The reaction was quenched by the dropwise addition of 1 ml cold H 2 O followed by addition of a cold brine and ether mixture. The organic phase was dried (MgSO 4 ) and the solvent removed leaving an oil. The product was purified via cold column chromatography (-10° C.) on Florisil, eluting with 4% Et 2 O/96% C 6 H 14 . The purified product 82 mg (85%) was not stable at room temperature for periods longer than a few hours.
Reaction of Compound F with Ag + /H 2 O 2
In 6.6 ml of dry ethyl ether at 0° C. was dissolved 40 mg (0.1 mmol) bromide (F). To this solution was added 0.95 ml 90% H 2 O 2 (36.3 mmol) in one portion. The solution of F and H 2 O 2 was allowed to warm to slightly below room temperature and then 0.758 gm (3.5 mmol) of silver trifluoroacetate was added in one portion. A yellowish precipitate of AgBr formed almost immediately. The reaction was allowed to stir for five to ten min and then was quenched by the addition of a cold mixture of aqueous NaHCO 3 and ether. The ether solution was washed twice with the bicarbonate and then dried (MgSO 4 ). The products were purified via cold column chromatography (-10°) on Florisil eluting with 15% Et 2 O/85% C 6 H 14 . The two products isolated 25 mg (71%) gave a positive peroxide test to a ferrous thiocyanate spray reagent on TLC (silica gel plates, 50 % Et 2 O/50% C 6 H 14 ). The two products had identical HPLC elution order and retention volumes as the 12 and 8-hydroperoxy eicosatrienoic acid methyl esters synthesized previously.
Having now fully described the invention, it will be apparent to one of ordinary skill in the art that many changes and modifications can be made thereto without departing from the spirit or scope of the invention as set forth herein. | A nucleophile substituted unsaturated hydrocarbon based compound is prepared by reacting a compound of the formula: ##STR1## wherein R and R' are hydrogen, alkyl, alkenyl, cycloalkyl, cycloalkenyl, aryl, aralkyl, alkoxyalkyl, alkoxy, alkylthioalkyl, or carboxyalkyl or carboxyalkenyl and X is a leaving group selected from the group consisting of chlorine, bromine, and iodine with a nucleophilic reagent. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The field of the invention is directed to the provision of a simple yet highly effective method of and means for providing A.C. motors with an infinitely adjustably output torque within the limits of zero to full nameplate rating.
2. Description of the Prior Art
Applicant is aware of the following patents which, in his opinion, are most relevant to the subject invention.
U.S. Pat. No. 2,748,334 to G. L. Miller dated May 29, 1956 discloses two variants of a VARIABLE SPEED INDUCTION MOTOR wherein means are provided for imparting endwise axial movement to the stator 26 relative to the outer periphery of rotor 12 for selectively varying the amount of magnetically responsive flux introduced into the magnetic field at any time by the stator. The rotor is provided with a first portion 18 and a second portion 20 wherein the portion of the circumference of portion 22 is cut away at 26 to provide an annular groove or gap which completely encircles the periphery of portion 22. This reference in FIGS. 4-7 also illustrates means whereby the rotor, per se, is mounted for endwise axial movement relative to the stator which is fixedly mounted relative to the inner surfaces of the motor housing.
The change in the axial relationship of the axially shiftable stator relative to the axially fixed rotor, or the change in the axial relationship of the axially displacable rotor relative to the axially fixed stator is utilized to alter the path for the stator flux in such a manner as to achieve a change in output speed of the rotor. The invention of the subject application is distinguishable from the disclosure of this reference since in applicant's device both the rotor and the stator are at all times fixed against a relative axial movement, and control of the flux is accomplished by advancing or retracting magnetic control rods axially into and out of control-rod-receptive channels provided through the stator.
U.S. Pat. No. 2,959,694 dated Nov. 8, 1960 discloses an ADJUSTABLE SPEED SQUIRREL CAGE INDUCTION MOTOR of the type which includes a stator which is axially shiftable relative to and along the length of the rotor for thereby altering the path of the stator flux to the rotor to control the rotational speed of the rotor wherein the rotor includes a low resistance induction section 19 which is disposed adjacent and in axial alignment with a high resistance induction section 20. The stator element 22 is provided with conventional polyphase windings 23 said stator being longitudinally slideable internally of the motor frame relative to the outer periphery of the rotor.
The operation of U.S. Pat. No. 2,959,694 is described in column 4, lines 24-50 as follows:
"In operation, at start, with the stator 22 over only the nondriving, noninductive rotor section 21, the latter provides a magnetic body of low reluctance acting as a shunting element for the stator field to maintain a high counter electromotive force in the stator winding and avoid undue current drain on the line. To start rotation of the rotor at low speed, the reversible control motor 33 is operated to move the stator from right to left (FIG. 1), gradually bringing the stator over the high resistance rotor section 20 to give the motor high starting torque with high slip and low current drain from the line. Then further operation of the control motor 33 to move the stator on over the low resistance section 19, further reduces the effective resistance of the combined driving rotor sections 19 and 20 gradually bringing the motor to a characteristic giving low slip and substantially constant speed with load changes."
"To reduce speed or bring the motor to a stop, the control motor 33 is reversed; moving the stator back toward the nondriving, rotor section until the desired reduction in motor speed is obtained, or all the way to the nondriving section if stoppage is desired. Intermediate positions of the stator will give intermediate speeds which may be maintained for a considerable time without undue heating due to the effective cooling system for dissipating heat generated in the windings, particularly the high resistance winding."
U.S. Pat. No. 4,025,840 to G. E. Brissey et al dated May 24, 1977 discloses a PERMANENT MAGNET GENERATOR WITH OUTPUT POWER ADJUSTMENTS BY MEANS OF MAGNETIC SHIMS which are designated by the numeral 11 and which, as clearly illustrated in FIGS. 1 and 3, are disposed in fixed, overlying relationship with the outer surface of nonmagnetic insulated wedges 24 which in turn overlie the upper portions of the slot liners 23 which encapsule coils 20, 21, and 22 wound around the pole stems located in compartments which are disposed in slots 12 between adjacent teeth 13 which extend radially from yoke 14 of the stator. The stator teeth 13 are of the salient or overhanging type and include a pair of oppositely extending salient tip portions 15. Magnetic shims 11 are inserted endwise into one or more of a plurality of the stator slots 12 being wedged beneath overhanging portions 15 of the stator teeth and the upper surface of the insulating wedge 24 after which the triangular ends 26 of the magnetic shims (not FIG. 2) are turned upward for engaging the opposite ends of tip portions 15 of a stator tooth 13 to thereby effectively prevent the endwise removal of a shim until and unless an upturned end 26 thereof has been bent downwardly back to the plane of the shim, per se, after which it may be slid endwise from between adjacent teeth 13.
This reference teaches that by the judicious selection and placing of shims in certain specific selected slots of the stator, the flux leakage between the stator and rotor at the location of the shims may be increased whereby the leakage inductance of the windings in those slots in which the shims have been placed will, under increased load, reduce the output from the selected windings without in any way effecting the output from the other windings of those particular slots which have not been provided with a magnetic shim strip 11.
U.S. Pat. No. 2,342,720 dated Feb. 29, 1944 to J. H. Blankenbuehler discloses a WELDING GENERATOR wherein the reluctance of the path of the magnetic leakage flux between the arcuate shoe member 19 and 20 and the field pole members 11 and 12 are selectively varied by means of a movable magnetic shunt member 34 which is positioned in bridged relation between the adjacent portions of the shoe members 19 and 20 and wherein the movable shunt member 34 is suitably mounted for endwise axial movement relative to said pole members, thereby changing the output welding current as delivered by the generator.
Abstract #209,189 published Apr. 21, 1953, of H. K. Ziegler discloses an ALTERNATING CURRENT MACHINE which has a stationary armature 33 with a winding thereon, a rotor 21 for producing a permanent magnetic field, and a housing 30. A laminated soft iron ring-shaped magnetic shunt member is supported coaxially of the rotor shaft 28 and is adjustably attached to the housing 30 and/or the rotor shaft 28. The ring-shaped magnetic shunt is adjustable axially of the rotor shaft by means of a suitable mechanism in order to vary the amount of flux from the permanent magnet rotor which links both the rotor and the armature winding. If desired a damper winding 27 may also be provided.
U.S. Pat. No. 978,638 to C. A. Parsons et al dated Dec. 13, 1910 relates to REGULATION OF DYNAMO ELECTRIC MACHINERY wherein the A.C. output voltage of a polyphase A.C. generator is regulated by providing a secondary winding for the leakage path of the flux.
U.S. Pat. No. 1,231,588 to L. T. Frederick et al dated July 3, 1977 discloses MAGNETIC MATERIAL from which magnetic shims are produced for reducing the eddy current loss in a stator or rotor by narrowing the air gap in the stator or rotor slot openings. The composite shim material is composed of both nonmagnetic and magnetic material.
Applicant is also aware of the disclosure of German Pat. No. 817,008 310/190--German Pat. No. 233,235 310/190--and German Pat. No. 159,241 310/190, and he is also aware of U.S. Pat. No. 3,226,582 to S. Beckwith dated Dec. 28, 1965 which discloses ADJUSTABLE TORQUE INDUCTION MOTORS and U.S. Pat. No. 3,042,820 dated July 3, 1962 to A. Diamond which discloses a SERVO MOTOR WITH ADJUSTABLE VELOCITY DAMP. However, it is considered that none of the last 5 mentioned references are as relevant as any of the first seven mentioned references, the disclosures of which have been more fully discussed hereinabove.
The disclosure of none of the 12 aforementioned references when considered singly or in combination neither teach nor disclose the inventive concept for accomplishing the concept of torque control of an alternating motor as disclosed in this application, nor is the invention of this application obvious, as that term is used in U.S. C. Title 35, Section 103.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a partial end view partly in section illustrating the relationship between the stator and rotor of a typical, or conventional, A.C. motor, showing the path of magnetic flux between the stator to the rotor.
FIG. 2 is a view generally similar to FIG. 1 but from which it differs in that it illustrates and embodies the inventive concept of the present invention.
FIG. 3 graphically illustrates the relationship between current-torque and the rotor r.p.m. of an A.C. motor which embodies the teachings of the present invention.
FIG. 4 graphically illustrates the relationship between the torque and r.p.m. of an A.C. motor which embodies the teachings of the present invention.
FIG. 5 is a perspective view illustrating the torque-control-rods and the manner in which they are anchored to a common mounting-control ring.
FIG. 6 is a vertical sectional view through one end-adjacent portion of a typical A.C. motor, the housing of which has been extended to accommodate the overall length of endwise, axial travel of the torque-control-rods of FIG. 5 in their respective elongate channelways through the stator, and which further illustrates manually operable means for selectively advancing or retracting the control rods relative to the stator.
DETAILED DESCRIPTION OF THE INVENTION
By way of background, and with particular reference to FIG. 1, the relationships between the stator and the rotor of a conventional electric A.C. motor have been illustrated as representing prior art, wherein the letter a designates the stator yoke; S stator slots in the yoke in which slots the primary windings S' of the stator are housed; b stator teeth which are disposed between adjacent stator slots; c the air gap between the adjacent peripheral surfaces 10 and 12 of the stator yoke a and the rotor yoke e. Rotor yoke e is provided with a plurality of circumferentially spaced U-shaped rotor teeth d which are defined by open ended slots f which are open at their outer ends to air gap c, and each of slots f house a rotor bar g.
The stator a is suitably anchored by any suitable means, not illustrated, relative to the interior of the motor housing 60, FIG. 6, whereas the rotor yoke e is secured to and carried by a drive shaft 30 the opposite ends or end-adjacent portions of which are rotatably mounted in bearings. It should be understood that one end of shaft 30 projects axially from and beyond an end of the motor housing as conventional in electric motors.
It should be understood that for ease of understanding only one of the slots of the stator and rotor have been provided with coils, and magnetic members are associated with all of the slots S and f.
FIG. 1 illustrates the flux path between the stator and rotor of the conventional or prior art A.C. electric motors.
Classical theory states that the magnetic flux originating in the stator windings S' of an A.C. motor provides a magnetic coupling with rotor bars g, and that flux which does not penetrate the air gap c does not contribute to turning torque of the rotor.
Referring again to FIG. 1 it will be noted and understood that the lines of flux indicated by φ 1 and φ 2 contribute to rotor torque, it being noted that the output torque of the rotor is proportional to the square of this flux density, whereas lines of flux φ 3 do not contribute to rotor torque.
The most widely used methods of reducing flux φ 1 for providing reduced starting current, reduced torque, or reduced speed has been to reduce the primary, that is the stator winding voltage by means of an auto transformer, solid state SCR Controller or some other suitable voltage reducing device.
The present invention, as illustrated in FIG. 2, relates to a method of and means for selectively changing the proportion of the flux of φ 1 and φ 3 without changing the applied stator voltage. Maximum torque in rotor shaft 30 is accomplished when φ 1 is a maximum and φ 3 is minimum, and conversely minimum torque is accomplished when φ 1 is minimum and φ 3 is maximum.
In FIG. 2 the overall shape of the stator slots are defined by an inner channelway 2m and a radially spaced outer channelway 2S, and a pair of air gaps 2h 1 and 2h 2 , wherein air gap 2h 1 is narrower than and extends between said inner and outer channelways, and wherein inner air gap 2h 2 is narrower than and extends between said inner channelway to the inner periphery 10 of the stator in open communication with air gap 2c between the adjacent surface 10 and 12 of stator and rotor.
Torque control rods 2r fabricated from magnetic material are dimensioned to make a snug, but slip fit with the interior of the inner channelways 2m, said rods being of an overall length whereby to extend the full length of the inner channelways when disposed in a fully advanced position within and relative to the stator yoke.
Since the magnitude of the flux φ 1 , φ 2 , and φ 3 of FIG. 1 and 2φ 1 and 2φ 3 of FIG. 2 are dependent upon their respective path resistance, the highest flux resistance is defined by the air gaps c and 2c.
In FIG. 2 the outer channelway 2S is provided with turns or windings 2S'. The inner channelway 2m may be empty, in which event it constitutes part of an overall air gap 2h 1 , 2hm, and 2h 2 , or said inner channelway may be partially or completely filled with a magentic rod 2r.
In order to change the relationship of flux 2φ 1 to flux 2φ 3 the magnetic flux path resistance is changed by moving rods 2r in their respective channelways. With the rods withdrawn the air gap of 2φ 3 is defined as 2h 1 , plus 2hm plus 2h 2 , whereas flux 2φ 1 has but two air gaps, viz 2c. Therefore, with the inner channelways empty the magnetic path of flux 2φ 3 has a substantially greater resistance than the magnetic path of flux 2φ 1 and maximum turning torque will be applied to the rotor.
However, with the inner channelways filled with magnetic rods 2r, the magnetic path of flux 2φ 3 has a lower magnetic resistance than flux path 2φ 1 and the output turning torque of the rotor will be a minimum because the flux is, in effect, short circuited through said rods.
In FIG. 3 curve T 1 is a typical Nema curve as occurs when flux 2φ 1 is at a maximum.
If the flux 2φ 1 is reduced by one-half by inserting the magnetic rods 2r into the inner channelways of the stator the torque of the motor rotor will be reduced to one-quarter of maximum torque 2φ 1 as indicated by curve T 2 .
It has also been established that whenever flux 2φ 3 and 2φ 1 are equal, in FIG. 2, the output turning torque of the rotor will be one-quarter rated torque of the motor.
FIG. 3 further discloses that the maximum torque T 1 has a corresponding maximum starting current I 1 , and the relative values of starting current I 2 for torque T 2 has been indicated.
With the magnetic control rods 2r inserted longitudinally into their respective inner channelways 2m to a point where the flux 2φ 1 equals the flux 2φ 3 , the starting current will be approximately one-half of the maximum starting current, and the starting torque will be approximately one-quarter of the maximum starting torque T 1 . Under these conditions it is noted from FIG. 3 that a typical load curve L 1 intersects the reduced speed-torque-curve T 2 at RPM 2 , and that the said load curve L 1 intersects the maximum torque-curve T 1 at RPM 1 when the magnetic rods 2r are completely withdrawn from their channelways in the stator.
FIG. 4 shows that with the magnetic control rods of FIG. 2 withdrawn from the stator, and with 2φ 1 at maximum, a high slip motor will generate a speed-torque curve similar to T 3 . By inserting the magnetic control rods longitudinally into slots 2m FIG. 2 an infinite family of speed-torque curves would be generated from T 3 to T∞. With a load curve similar to L 2 the insertion of the magnetic control rods will also generate an infinite variety of running speeds depending on where the load curve intersects the corresponding torque curve. The same would be true of loads similar to L 3 and L 4 .
The configuration of the magentic torque-control rods could be any shape as long as they fill their respective channelways 2m. As earlier noted, it is important to have close physical contact between the adjacent surfaces of the magnetic rods and channelways 2m FIG. 2. These magnetic rods may be solid or laminated similar to the stator. The size of the inner channelway 2m will be dependent on the rotor output torque range requirements. The stator is wound in a conventional manner with coils inserted through openings 2h 2 , 2hm, and 2h 1 . Openings 2h 1 and 2h 2 will be sized in accordance with conventional motor design practice. Dimension 2hm FIG. 2 will be sized according to magnetic control rods selected.
The length and number of the magnetic control rods is contingent upon degree of torque variations required. Maximum usable rod length would be insertion to the total length of the stator, and the number of magnetic control rods would normally be the same as the number of stator slots, but this again is optional depending on range of desired control.
As best illustrated in FIG. 5 one end of each of the control rods 2r are fixedly secured to the inner planar surface 40 of a common mounting-control ring 42 such as, by way of example, welding W, or the like. Each of the rods are disposeds in exact parallel axial alignment whereby to be slideably received into corresponding inner channelways 2m of the stator.
Endwise axial movement may be imparted to ring 42 and rods 2r by any suitable means, such as, by way of example, a jackscrew J which threadably engages member 50 which spanningly engages the free outer ends of a pair of actuator shafts 52 whose opposite ends are suitably anchored to the mounting control ring 42.
One end of a conventional motor housing 60 may be extended by removing the conventional bell cap and replacing it with a cup-shaped housing element 61 having side walls 62 and an end wall 64, wherein the inner surface of the said end wall is spaced from the adjacent end of housing 60 by a dimension or distance to freely accommodate the position of ring 42 when the rods have been fully retracted from their channelways 2m of the stator.
End wall 64 may be provided with an inwardly projecting boss 66 in which a bearing 68 in which the end of the rotor shaft 30 is journaled.
One end of the jackscrew, which threadably engages the internally threaded bore 54 of a strut member 50, may be rotatably secured to said member by an opening in the center of a plate 56 through which reduced shank 57 of the jackscrew projects, the outer end of said shank being engaged by a washer 58 which is anchored to the shank by means of a set screw 59. The plate 56 may be securely though releaseably fastened to rear wall 64 as at 69.
The opposite end of the jack shaft may be engaged by a handle K, whereby rotary motion imparted to the jack shaft is translated into endwise axial movement of the magnetic torque-control rods 2r.
The subject invention is ideally suited for use with both single phase and polyphase A.C. motors with conventional stator windings modified to include channelways such as 2m for the reception of torque-control rods 2r.
Rods 2r may, in some instances, be introduced into the conventional stator slots S, as in FIG. 1, in those instances where the windings S' therein do not completely fill slots S to provide an open space beneath the windings into which the rods may be inserted. However, in each instance it is imperative that the rods are disposed between the windings as S' of FIG. 1 or 2S' of FIG. 2 and the air gap between the slots or channelways in which the rods are received and the air gap c or 2c, respectively, between the adjacent peripheral surfaces of the stator and rotor.
In some cases it may be desirable to provide a control rod for each of the stator slots, whereas in other instances rods may be associated with alternate or every third slot.
It should be understood that the inventive concept of this application is not limited to any particular means for imparting endwise axial movement to the control rods 2r and that the means illustrated in FIG. 5 merely represent one type of means which may be utilized. The desired movement to said rods can be manual, pneumatic, hydraulic, electromechanical, or they may be activated statically or dynamically by close loop feed back transducer.
It should likewise be understood that the particular shape of the elongate control rod-receptive open spaces or channelways of the stator slots and the complimentary shape of the control rods need not be rectangular as illustrated in the figures, but may be of any one of a plurality of other shapes. | Alternating Current (A.C.) Motors are modified in such a way as to provide zero to full nameplate torque, by inserting magnetic rods into elongate control-rod-receptive channelways in the stator. By moving the rods in and out of their respective channelways the magnetic path of the stator flux will change. With the rods all the way out of the stator full nameplate torque is achieved. As the rods are inserted deeper into the stator, the output torque of the rotor will decrease proportionally to a minimum value. | 7 |
FIELD OF THE INVENTION
The invention relates to a lock-flanged hinged nailing fin made entirely of polypropylene for mounting window installations or assemblies to a surrounding supporting structure, such as the wall of a house.
DESCRIPTION OF THE PRIOR ART
Nailing fins for attaching window assemblies to wall structures of a house or building being constructed are known and have been utilized for some time in the home building industry. Generally speaking, the fins or bands or strips of stiff material such as metal or plastic are attached along one elongated edge to the periphery of the frame of the window assembly and have holes through which nails are placed to attach the fin to the surrounding supporting structure in order to hold the window assembly in place.
In the case where a wing or flange is formed integrally with the nailing section of the nailing fin to extend out over a hinge section thereof, the hinged section is made of different material than the nail fin itself and this necessitates the use of dual extruders and give rise to dual durometer materials being formed during the extrusion process of making the hinged nailing fin. U.S. Pat. No. 4,821,472 typifies the hinged nailing fin prepared using two separate extruders wherein the hinged nailing fin is made of two different plastics and therefore is subject to higher cost in its manufacture.
While such a hinged construction provides numerous advantages, the hinged nailing fin of the prior art having a wing or flange formed integral with the nailing section has the disadvantage of affording no protection against the window being blown out during a period of high winds or forced out as a result of, for example, a person washing the window from the inside and leaning on the frame.
Therefore, a first need exists in this art to reduce costs by eliminating the dual durometer materials occasioned by the use of two separate extruders to make the hinged nailing fin in which the elongated strip section is made of one plastic material and the flexible hinge section is made of a different plastic material. A second need exists to provide some assurances against having a window blow out or forced out once the hinged nailing fin having the wing or flange formed integral therewith has been used to install the window frame into an opening in the wall of a building being constructed.
SUMMARY OF THE INVENTION
It is therefore an object of the invention to overcome deficiencies in the prior art, such as indicated above. It is another object of the invention to provide improvements in window frames having nailing fins.
The wing or flange nailing fin of the instant invention is an integrally formed polypropylene strip having a relatively wide and thin elongated polypropylene member containing nail holes for attaching the strip to a support structure, the narrow thin elongated polypropylene member having an elongated edge parallel and closely adjacent to the elongated edge of the first member, and a narrower thin flexible polypropylene member hingedly connecting the first and second members along their parallel adjacent edges in order to releaseably fold together the first and second members and means for attaching the second member to a side of a window assembly.
The wing or flange member formed integrally with the nailing section of the nailing fin and which extends out over the hinge section is provided with a tongue section which snap fits into a hook or groove section of the second elongated narrower thin band or strip of polypropylene material, in order to form a lock which prevents the window from being blown out or forced out. The nailing fin may be attached to the window assembly in any suitable way, such as by resting or placing one edge in an elongated kerf or in an elongated T-shaped groove in the frame of the window assembly with integrally formed flexible plastic barbs holding it securely to the window assembly, and this avoids the use of stapling, nailing or using an adhesive to attach the nailing fin to the window frame.
BRIEF DESCRIPTION OF THE DRAWING
FIG. 1 is a perspective view of a window assembly with the attached nailing fin of the invention;
FIG. 2 is a sectional view taken along line A--A of FIG. 1 illustrating the preferred embodiment of the invention;
FIG. 3 is a perspective view of a preferred embodiment of the invention; and
FIG. 4 is a sectional view taken along the line B--B of FIG. 3.
DETAILED DESCRIPTION OF THE INVENTION
FIG. 1 depicts a window assembly, designated by numeral 2, and made up of a pane of glass 10 within a vinyl plastic, aluminum, or wood frame 11 which may be clad in a plastic or metal outer protective layer. Nailing fins 12 are attached to the outer edge of the window frame 11. Installation is effected by inserting the window assembly into an opening in the wall of a house or building, so that nailing fins 12 are rested against the surrounding supporting structure. At this point, nails (not shown) are driven through the nail holes 13 into the structure in order to firmly hold the window assembly in place.
The depiction in FIG. 1 illustrates the amount of space needed if the window assembly is shipped with the nailing fins attached thereto. It is clear from this figure that a shipping container must be sufficiently large to accommodate the additional space needed for the nailing fins and also provide more protection against damage to the nailing fins.
In the preferred embodiment of the invention as seen in FIG. 2, the nailing fins 12 stand outwardly or laterally from the frame 11 and secure nails (not shown) inserted through the nail holes 13 into the supporting frame structure (not shown).
As can be seen from FIGS. 2, 3 and 4, the nailing fin of the invention has an elongated thin wide section 14 made of polypropylene, with nailing holes 13 therein. The second narrower section 15 of polypropylene material extends in parallel relationship to member 14 along one edge and members 14 and 15 are adjoined together along their adjacent edges by an extremely narrow strip or hinge-band 16 of flexible polypropylene material.
In the preferred embodiment, section 15 is of a L-shaped configuration and has a groove or hook 17 on a short extension thereof which is in parallel relationship with elongated wide section 14. Groove or hook portion 17 permits a tongue portion 18 on the distal end of the wing or flange 19 to be snapped in place. Section 15 has a leg 20 which is inserted in a kerf 21 in the outer frame 11 of the window assembly. Resilient polypropylene barb-shaped lengths or projections 22 extend out along each side of leg 20 and serve to grip the inner walls of the kerf 21 to firmly hold leg 20 in the nailing fin attached to the window assembly.
While this is one method of attaching the nailing fin, it is to be understood that the nailing fin may be attached with a suitable adhesive or stapled or nailed to the outside edge or periphery of the window frame.
It is clear that the nailing fin 12 is integrally formed in one piece, extruded from a single die, and all of the sections and parts, i.e. the nailing section 14, second narrower section 15, hinged or extremely narrow strip or hinge-band 16, and the barbs 22, are extruded in a single extrusion process, and the entire nailing fin including the hinged section 16 and the groove and tongue section which form the latch hook are all made of polypropylene. While the invention is described in conjunction with the nailing fin 12 being formed of polypropylene because polypropylene has unique or almost unique characteristics which provide both sufficient rigidity and good hinge properties, it will be understood that other specially engineered materials having the same properties could be used in place of polypropylene.
It is clear from the dashed line in FIG. 2 that nailing section 14 of the nailing fin may be folded up along the hinge line which defines the narrow strip or band 16 in order to enable it to rest along the side of frame 11 of the window assembly and thereby occupy little additional space when the window assembly is attached to the nailing fin and placed in a carton or container for shipping.
Wing or flange 19 is formed integrally with the nailing section 14 of the nailing fin and extends out over the hinge section or extremely narrow strip 16. In this arrangement, protection is provided for the hinge section when the nailing fin is in place and this also serves to ensure that the nailing section is kept lateral with the window assembly. The latch hook section formed by groove or hook 17 and tongue 18 formed respectively integrally with the second narrower section 15 and the wing or flanged section 19, allow the latch hook to snap in place to thereby provide assurances against pushing out the window assembly from the inside of the house or building if a party is leaning against it. This novel arrangement also prevents the window from being blown out in a inclement weather environment in which high winds prevail.
The foregoing description of the specific embodiments will so fully reveal the general nature of the invention that others can, by applying current knowledge, readily modify and/or adapt for various applications such specific embodiments without departing from the generic concept, and, therefore, such adaptations and modifications should and are intended to be comprehended within the meaning and range of equivalents of the disclosed embodiments. It is to be understood that the phraseology or terminology employed herein is for the purpose of description and not of limitation. | A foldable nailing fin for a window assembly having hingedly attaching strips along adjoining edges for releasably folding two elongated strips, wherein the strips and means hingedly attaching the strips are made of polypropylene, and a flange member extending from a first strip over the hingedly attaching means toward a second strip has a tongue section on a distal end which forms a latch hook with a hook section on a second elongated strip. | 4 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] The present invention relates to a refillable melody candle, and more particularly, to a refillable melody candle in which a seated plate having a sensor and a melody chip built therein is coupled to the bottom of a body of the candle in such a manner as to be removably coupled to a separate base having a power supply section and a driving controller built therein.
[0003] 2. Background of the Related Art
[0004] In general, a melody candle includes a body 10 formed into a solid state by solidifying a combustible material, and a wick 11 interposed in the center of the body and made in such a manner that natural fibers or chemical fibers are processed in the form of threads or fabrics and then twisted in the form of spiral knitting yarn.
[0005] An optical transmission member 13 for transmitting light of a flame 12 generated during the combustion of the wick is interposed inside of the wick 11 . The optical transmission member 12 is configured with an optical fiber used as a transmission line for optical communication.
[0006] The melody candle also includes a base portion 20 having a seated plate 20 a formed at the top thereof for seating and fixing the bottom portion of the body 10 , a volume adjust button 21 mounted at one side thereof for gradually adjusting volume level of the melody candle, and a battery container formed at a predetermined position therein for receiving batteries 22 .
[0007] A printed circuit board (PCB) 24 , which has a melody storage chip 26 for storing various melodies classified by genre, an optical sensor 25 as on/off means for playing back sounds stored in the melody storage chip 26 , etc., mounted thereon, is installed within the base portion 20 . At this time, the optical sensor 25 is positioned to be oriented vertically toward the lower end portion of the optical transmission member 13 interposed inside of the wick so as to receive light emitted from the optical transmission member.
[0008] A flame intercepting member 14 made of a metal material is disposed at the lower portion of the wick 11 so as to prevent the wick from being burnt.
[0009] When the tip of the wick 11 of the melody candle A constructed as above catches fire, it becomes ignited while generating flame. At this time, light emitted by the flame is downwardly transmitted to the optical sensor 25 positioned vertically via the optical transmission member 13 interposed inside of the wick such that the optical sensor 25 may receive the light.
[0010] Thereafter, the light sensor detects the received light and supplies power from batteries to the melody storage chip 26 . Then, the melody storage chip outputs various melody sounds stored therein so as to play back them through a loudspeaker 23 .
[0011] However, for the above conventional melody candle, there has been a problem in that since the body of the candle and the base portion for generating melodies are integrally formed with each other, it is difficult for general users to replace a burnt-out candle used with a new one.
[0012] To this end, there has been developed a technology which enables replacement of a candle used with a new one. As shown in FIG. 2 , two different twisted metal wires are jointed together such as thermocouple so as to sense flame of a candle. Electromotive force effect generated between the two metal conductors when heat is applied to the junctions of the metal wires, is used as Seeback effect. The conductors are configured in such a manner as to be thin enough to be burnt by flame of the candle, and hence can be burnt together with the candle wick 6 . In order to transmit electromotive force generated from the candle wick 6 during the burning of the candle to the a sound playback device, a metal wire 1 and a metal wire 2 used as conductors in FIG. 2 is soldered to a circuit board 3 having two concentric circular electrodes 4 and 5 , respectively. This structure is made in such a manner that the two electrodes 4 and 5 mounted on the bottom surface of the candle are in contact with the sound playback device disposed within a separate support.
[0013] However, since such a conventional technology employs Seeback back, each of the metal wires is not molten well during the heating of it, such that it may be exposed to the outside of the candle. In addition, long term use of the metal wires contributes to soot production, which in turn deteriorates quality of the candle. Further, since this prior art is only a method in which a burnt-out candle is replaced with a new one, a melodies stored in the sound playback device are always outputted in a uniform pattern, which may allow a user to feel a repugnance to the candle in use during a for long time.
SUMMARY OF THE INVENTION
[0014] Therefore, the present invention has been made in view of the above problems, and it is an object of the present invention to provide a melody candle in which a seated plate has a melody chip for generating a unique melody sound built therein and is coupled to the bottom of a candle body in such a manner as to be removably coupled to a separate base, such that when the candle is ignited it outputs its own unique melody sound from the melody chip.
[0015] Another object of the present invention is to provide a melody candle in which different melody sounds are stored in melody chips built in the seated plates of respective candles, to thereby satisfy various desires of users according to season, weather, sex and taste.
[0016] Another object of the present invention is to provide a melody candle in which a fitting recess is formed on the central bottom portion of a candle body such that a coupling cap is pressedly fitted into the fitting recess while being coupled with a coupling part formed on a seated plate, to thereby facilitate both the coupling between a candle body and the seated plate and the fixing of a candle wick.
[0017] To accomplish the above objects, according to the present invention, there is provided a refillable melody candle comprising: a body; a seated plate including a coupling part protruded from a central upper surface thereof so as to fix a wick which is interposed inside of the body and has an optical transmission member built therein at the bottom surface of the body, an optical sensor disposed at a corresponding portion of the lower end of the optical transmission member, a melody chip coupled to the optical sensor, the optical sensor and the melody chip being received in the seated plate, power terminals mounted on the underside thereof such that they can be interlocked with the optical sensor upon the actuation of the optical sensor, an output terminal of the melody chip; and a base including a receiving recess formed on the upper surface thereof for receiving the seated plated and the bottom portion of the body therein, base terminals mounted on the bottom surface of the receiving recess to be electrically conducted with the power and output terminals, respectively, a controller and a power supply section disposed inside thereof for outputting a predetermined melody via the respective base terminals, whereby a melody is generated from the base coupled to the bottom portion of the candle when the optical sensor senses flame of the candle via the optical transmission member.
[0018] According to the present invention, the seated plate having the optical sensor and the melody chip is coupled to the bottom surface of the candle body, the candle including the seated plate is removably received within the receiving recess of the base, the base amplifies a melody sound to output it to the outside via the seated plate, and the base terminals are protruded from the top surface of the receiving recess to enable electrical connection of the base terminals to the output terminal of the seated plate upon the contacting between the base terminals and the output terminal of the seated plate. Further, the coupling part is formed protrudedly on the central top surface of the seated plate such that the seated plate can be easily coupled to the bottom surface of the candle body with the coupling part being fitted into the coupling cap.
BRIEF DESCRIPTION OF THE DRAWINGS
[0019] The above and other objects, features and advantages of the present invention will be apparent from the following detailed description of the preferred embodiments of the invention in conjunction with the accompanying drawings, in which:
[0020] FIG. 1 is a longitudinal sectional view illustrating a general melody candle;
[0021] FIG. 2 is a schematic perspective view illustrating essential parts of another example of a general melody candle;
[0022] FIG. 3 is a longitudinal sectional view illustrating a refillable melody candle according to the present invention;
[0023] FIG. 4 is a circuit diagram illustrating the construction of the refillable melody candle according to the present invention;
[0024] FIG. 5 is an exploded perspective view illustrating essential parts of the refillable melody candle according to the present invention;
[0025] FIG. 6 is a longitudinal sectional view illustrating an assembled state of essential parts of the refillable melody candle according to the present invention; and
[0026] FIG. 7 is a longitudinal sectional view illustrating another assembled state of essential parts of the refillable melody candle according to the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0027] Reference will now made in detail to the preferred embodiment of the present invention with reference to the attached drawings.
[0028] FIG. 3 is a longitudinal sectional view illustrating a refillable melody candle according to the present invention.
[0029] Referring to FIG. 3 , there is shown a refillable melody candle including a body 10 , a seated plated 30 and a base 40 .
[0030] The seated plate 30 includes a coupling part 34 protruded from a central upper surface thereof so as to fix a wick 11 which is interposed inside of the body 10 and has an optical transmission member 13 built therein at the bottom surface of the body, an optical sensor 31 disposed at a corresponding portion of the lower end of the optical transmission member 13 , a melody chip 32 coupled to the optical sensor 31 , the optical sensor and the melody chip being received in the seated plate, power terminals P 1 ′ and P 2 ′ mounted on the underside thereof such that they can be interlocked with the optical sensor 31 upon the actuation of the optical sensor 31 , an output terminal P 3 ′ of the melody chip 32 .
[0031] The base 40 includes a receiving recess 41 formed on the upper surface thereof for receiving the seated plated 30 and the bottom portion of the body 10 therein, base terminals P 1 , P 2 and P 3 mounted on the bottom surface of the receiving recess 41 to be electrically conducted with the power and output terminals P 1 ′ P 2 ′ and P 3 ′, respectively, a controller 42 and a power supply section B disposed inside thereof for outputting a predetermined melody via the respective base terminals P 1 , P 2 and P 3 .
[0032] The melody candle further includes a coupling cap 16 having a fixing hole 18 formed therein to be coupled with the outer circumferential surface of the coupling part 34 and having a hook protrusion 17 formed on the outer circumferential surface thereof to be fixedly fitted into a fitting recess formed at the central bottom surface of the body 10 . The coupling cap 16 also serves to internally cap a pressed fixing member 15 mounted at the lower end portion of the wick 11 for pressedly fixing the wick together with the coupling part 34 .
[0033] FIG. 4 is a circuit diagram illustrating the construction of the refillable melody candle according to the present invention.
[0034] Referring to FIG. 4 , the terminals P 1 ′, P 2 and P 3 ′ of the seated plate 30 and the terminals P 1 , P 2 and P 3 of the base 40 are correspondingly coupled to one another in such a manner as to be in contact with one another. The seated plate 30 includes an optical sensor 31 such as a photo coupler for sensing light via the optical transmission member, i.e., an optical fiber of FIG. 3 , and a melody chip 32 for being supplied with power through the power terminal P 1 ′ upon the actuation of the optical sensor 31 and applying the supplied power to the output terminal P 3 ′.
[0035] The base 40 includes a controller 42 which has an amplifier 43 for receiving the output sound from the melody chip 32 via an input terminal P 3 connected to the output terminal P 3 ′ of the seated plate 30 and amplifying the output sound to output it, a variable resistor 44 for variably adjusting the amplified sound from the amplifier 43 to output it, and a speaker 45 for outputting the adjusted sound from the variable resistor 44 as a audible signal to the outside. Of course, the power supply section B such as a battery contained in the base 40 is used as a needed power source, but an adapter for rectifying AC power into DC power may be used, if necessary. Although there has been described the sensing of flame of the candle via the optical fiber 13 and the optical sensor 31 herein, the sensing of flame may be implemented by other sensing methods (known equivalent means such as Seeback, glass fiber, thermal conduction, etc.).
[0036] FIG. 5 is an exploded perspective view illustrating essential parts of the refillable melody candle according to the present invention.
[0037] Referring to FIG. 5 , a coupling part 34 is protruded from a central upper surface of the seated plate 30 such that a wick 11 and an optical transmission member 13 are placed on the coupling part. A coupling cap 16 has a fixing hole 18 formed therein for internally capping, a pressed fixing member 15 mounted at the lower end portion of the wick to pressedly fix the wick, together with the coupling part 34 , such that it may be fitted around the outer circumferential surface of the coupling part 34 . A hook protrusion 17 is formed on the outer circumferential surface of the coupling cap 16 to be fixedly fitted into a fitting recess 10 - 1 formed at the central bottom surface of the candle body 10 . The coupling part 34 also has an optical fiber inserting hole 35 for inserting the optical transmission member 13 thereto so as to guide the optical transmission member 13 toward the optical sensor 31 .
[0038] FIG. 6 is a longitudinal sectional view illustrating an example of an assembled state of essential parts of the refillable melody candle according to the present invention.
[0039] Referring to FIG. 6 , the candle body 10 has a recess 10 - 2 formed on the bottom surface thereof for receiving the seated plate 30 therein in such a manner that the bottom surface of the body is flush with the bottom surface of the seated plate 30 . The coupling cap 16 is so structured that it is slidably fitted into the fitting recess 10 - 1 formed at the central bottom surface of the body. The top end portion of the fixing hole 18 defining the inner diameter of the coupling cap 16 forms a pressing plate 19 having a pressing hole 19 - 1 formed therein. The diameter of the pressing hole 19 - 1 is smaller than that of the fixing hole 18 so that the wick 11 and the optical transmission member 13 are tightly inserted into the pressing hole to be received within the coupling cap 16 .
[0040] FIG. 7 is a longitudinal sectional view illustrating another example of the assembled state of essential parts of the refillable melody candle according to the present invention.
[0041] As shown in the drawing, the construction of FIG. 7 is identical to that of FIG. 6 except that the body 10 does not have the recess 10 - 2 of FIG. 6 formed on the bottom surface thereof, and different from that of FIG. 6 in that the seated plate 30 has a peripheral dam 36 formed at the outer circumference thereof in such a manner as to be extended slantingly upward from the outer circumferential surface thereof so as to correspondingly encircle a bottom peripheral portion of the body 10 .
[0042] According to the present invention constructed as above, the actuation of a switch SW applies power supplied from the power supply section B such as a battery, etc., to the seated plate 30 via the base 40 . At this time, when a user lights the tip of the wick 11 , the optical sensor 31 of FIGS. 3, 4 , 6 and 7 is operated via the optical transmission member 13 such as an optical fiber. When the optical sensor 31 is operated, a bias voltage from the power supply section B is applied to the seated plate 30 such that battery power of the power terminal P 1 ′ drives the melody chip 32 via a collector terminal of the optical sensor 31 which is called a photo coupler. The melody sound outputted from the melody chip 32 is supplied to the input terminal P 3 of the amplifier 43 which in turn amplifies the melody sound to a corresponding sound level to output the amplified sound to the outside through the speaker 45 . Of course, the volume of the sound may be adjusted by the variable resistor 44 , if necessary.
[0043] When the candle is burnt out after a lapse of the certain time period, a remaining portion of the candle body 10 coupled with the seated plate 30 is replaced with a new separate candle set coupled with a seated plate such that a user can hear another new melody sound. To this end, as shown in FIG. 5 , the pressed fixing member 15 presses and fixes the lower end portion of the wick 11 having the optical transmission member 13 , after which a part of the optical transmission member 13 extended downwardly from the bottom surface of the pressed fixing member 15 alone or/and the wick 111 is/are tightly inserted into the optical fiber inserting hole 35 of the coupling part 34 . In this case, there is of course used the seated plate 30 having the optical sensor 31 and the melody chip 32 built therein as shown in FIGS. 3, 6 and 7 . Then, the lower end portion of the optical transmission member 13 is disposed opposite to the optical sensor 31 . The coupling cap 16 is moved downwardly from the upper end portion of the wick 11 to the lower end portion thereof along a longitudinal direction of the wick in such a manner as to fit around the wick through the fixing hole 18 thereof, so that it can press the coupling part 34 to encircle the pressed coupling part therein or can be threadedly coupled with the coupling part 34 . At this time, the fixing hole 18 of the coupling cap 16 preferably has threads formed on the inner circumferential surface thereof to enable the coupling part 34 to be engaged with the coupling cap 16 or has protrusions formed on the inner circumferential surface thereof to enable the coupling part 34 to be pressedly fitted into the coupling cap 16 . Then, the pressing plate 19 formed on the top end of the fixing hole 18 presses against the bottom surface of the pressed fixing member 15 to securely fix the wick 11 . Thereafter, the coupling cap 16 previously coupled with the coupling part 34 is pressedly fitted into the fitting recess 10 - 1 as shown in FIGS. 6 and 7 . Although the fitting of the coupling cap 16 into the fitting recess 10 - 1 has been easily and simply performed by the pressing action of the hook protrusion 17 of the coupling cap 16 , the seated plate 30 is prevented from being separated from the body 10 to thereby ensure stability in use. In addition, only the simple fitting action enables an assembly between the seated plate 30 and the candle body 10 to thereby shorten the assembly time for the candle. Further, like in FIG. 6 , the seated plate 30 is adapted to be received within the bottom recess 10 - 2 of the body 10 upon the coupling between the seated plate 30 and the body 10 . Accordingly, the assembly structure as mentioned above can be used for a candle having a large diameter body. On the other hand, for a candle having a small or regular diameter body, a peripheral dam 36 is formed at the outer circumference of the seated plate 30 to correspondingly encircle and protect a bottom peripheral portion of the body 10 so as to improve durability of or prevent deformation of the bottom structure of the body.
[0044] As described above, a seated plate having a sensor and a melody chip built therein is coupled to the bottom of a body of the candle in such a manner as to be coupled/released to/from a receiving recess of a separate base. Accordingly, the base is kept as it is, and the candle body coupled with the seated plate is replaced with a new separate candle set coupled with a seated plate to thereby enable the refill of a candle which has been burnt out.
[0045] In addition, the melody candle of the present invention employs a technology in which the seated plate has a melody chip built therein, and hence different melody sounds are generated according to respective candles, to thereby satisfy various desires of users according to season, weather, sex and taste, which contributes to an increase in sale of candle products.
[0046] Further, a protrusion, i.e., a coupling cap is formed on the central top surface of the seated plate to fix a wick of the candle, and has a hook protrusion formed on the outer circumferential surface thereof to be easily fitted into a fitting recess formed at the central bottom surface of the candle body without a separate coupling tool.
[0047] While the present invention has been described with reference to the particular illustrative embodiments, it is not to be restricted by the embodiments but only by the appended claims. It is to be appreciated that those skilled in the art can change or modify the embodiments without departing from the scope and spirit of the present invention. | Disclosed is a refillable melody candle in which a seated plate having a sensor and a melody chip built therein is coupled to the bottom of a body of the candle in such a manner as to be removably coupled to a separate base having a power supply section and a driving controller built therein. The melody candle of the present invention has an economical effect in that it enables the re-use of the base in spite of replacement of a candle body. Further, the inventive melody candle may include a number of candle bodies, and the seated plates corresponding to the candle bodies includes melody chips having different melody sounds stored therein, respectively, such that a user can selectively hear various melodies. In addition, the use of the coupling cap for improving the coupling ability between the base and the body simplifies assembly process of the melody candle. | 5 |
BACKGROUND OF THE INVENTION
[0001] 1. Field of the Invention
[0002] This invention relates to computing systems, and more particularly, to efficient scheduling of speculative load instructions.
[0003] 2. Description of the Relevant Art
[0004] The pipeline depth of modern microprocessors continues to increase in order to support higher clock frequencies and increased microarchitectural complexity. Despite improved device speed, higher clock frequencies of next-generation processors limit the levels of logic to fit within a single clock cycle. The deep pipelining trend has made it advantageous to predict the events that may happen in the pipe stages ahead. One example of this technique is latency speculation between an instruction and a younger (in program order) dependent instruction. These younger dependent instructions may be picked for out-of-order (o-o-o) issue and execution prior to a broadcast of the results of a corresponding older (in program order) instruction. Additionally, the deep pipelining trend increases a latency to receive and use load (read) operation result data.
[0005] One example of the above instruction dependency and latency speculation is a load-to-load dependency. A younger (in program order) load instruction may be dependent on an older (in program order) load instruction. The older load instruction that produces the result data may be referred to as the producing load instruction. The younger instruction dependent on the result data of the producing load instruction may be referred to as the consuming load instruction. When the target register of an older producing load (read) instruction is also an address register (source operand) of a younger consuming load instruction, the occurrence may be referred to as pointer chasing. Linked list traversals typically include frequent pointer chasing.
[0006] For load (read) instructions, the requested data may be retrieved from a cache line within a data cache. Alternatively, the requested data may be retrieved from a store queue, such as in the case when control logic determines whether a load-store dependency exists. Data forwarding of load results to dependent instructions may occur by sending the retrieved data to a reservation station and/or a register file. Afterward, the data may be sent to one or more execution units corresponding to the younger dependent instructions. The data forwarding incurs an appreciable delay. The traversal of one or more linked lists within a software application accumulates this delay and may reduce performance. The latency for receiving and using load instruction result data may vary depending on instruction order within the computer program. However, the shorter latency cases may not be taken advantage of within a pipeline despite a high frequency of occurrence of the shorter latency cases. The traversal of a linked list is one case that may allow an opportunity to decrease the latency to use load instruction result data.
[0007] In view of the above, methods and mechanisms for efficient scheduling of speculative load instructions are desired.
SUMMARY OF EMBODIMENTS
[0008] Systems and methods for efficient scheduling of speculative load instructions are contemplated. In various embodiments, a processor includes a data cache, an execution core that executes memory access instructions, and a scheduler that issues instructions to the execution core. The execution core includes a load-store unit (LSU). The scheduler determines a first condition is satisfied. The first condition comprises result data for a first load instruction is predicted to reside in the data cache, rather than reside in a store queue in the LSU. Additionally, the first condition may include a LSU-internal forwarding condition comprising the step of predicting the result data for the producing load instruction is available directly from the data cache. The scheduler determines a second condition is satisfied, the second condition comprising a second load instruction younger in program order than the first load instruction is dependent on the first load instruction. In response to each of the first condition and the second condition being satisfied, the scheduler issues the second load instruction prior to the result data being available. In doing so, a load-to-load latency may be reduced. The LSU forwards the result data received from the data cache to address generation logic used to generate an address for the dependent second load instruction. For a series of load-to-load dependencies, such as a traversal of a linked list, performance of an application may significantly increase.
[0009] The scheduler may be coupled to a load-store (LS) predictor for predicting store-to-load dependencies. The LS predictor may store an indication indicating whether a store instruction with a dependent load instruction has already received result data. Therefore, the LS predictor predicts store-to-load dependencies whether or not the result data is already received within a store queue within the LSU. In order to determine result data for the first load instruction is not from a store queue within the LSU, and is predicted to reside in the data cache, the scheduler may determine the second load instruction has no allocated entry in the LS predictor. Should the result data be unavailable for the second load instruction when the second load instruction is ready for address generation, the second load instruction may be replayed.
[0010] These and other embodiments will be further appreciated upon reference to the following description and drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] FIG. 1 is a generalized block diagram of one embodiment of a computer program with data dependencies between load instructions.
[0012] FIG. 2 is a generalized block diagram of one embodiment of a processor.
[0013] FIG. 3 is a generalized flow diagram of one embodiment of a method for efficient scheduling of speculative load instructions.
[0014] FIG. 4 is a generalized flow diagram of one embodiment of a method for executing early scheduled speculative load instructions.
[0015] While the invention is susceptible to various modifications and alternative forms, specific embodiments thereof are shown by way of example in the drawings and will herein be described in detail. It should be understood, however, that the drawings and detailed description thereto are not intended to limit the invention to the particular form disclosed, but on the contrary, the intention is to cover all modifications, equivalents and alternatives falling within the spirit and scope of the present invention as defined by the appended claims. As used throughout this application, the word “may” is used in a permissive sense (i.e., meaning having the potential to), rather than the mandatory sense (i.e., meaning must). Similarly, the words “include,” “including,” and “includes” mean including, but not limited to.
[0016] Various units, circuits, or other components may be described as “configured to” perform a task or tasks. In such contexts, “configured to” is a broad recitation of structure generally meaning “having circuitry that” performs the task or tasks during operation. As such, the unit/circuit/component can be configured to perform the task even when the unit/circuit/component is not currently on. In general, the circuitry that forms the structure corresponding to “configured to” may include hardware circuits. Similarly, various units/circuits/components may be described as performing a task or tasks, for convenience in the description. Such descriptions should be interpreted as including the phrase “configured to.” Reciting a unit/circuit/component that is configured to perform one or more tasks is expressly intended not to invoke 35 U.S.C. §112, paragraph six, interpretation for that unit/circuit/component.
DETAILED DESCRIPTION
[0017] In the following description, numerous specific details are set forth to provide a thorough understanding of the present invention. However, one having ordinary skill in the art should recognize that the invention might be practiced without these specific details. In some instances, well-known circuits, structures, and techniques have not been shown in detail to avoid obscuring the present invention.
[0018] Referring to FIG. 1 , one embodiment of identification of data dependencies between load instructions in computer code is shown. As used herein, the data dependencies between load instructions may also be referred to as load-to-load dependencies. Table 100 illustrates an example of computer program instructions with load instructions dependent on other instructions for source operand data. The source operand data is used to generate an address for a memory read access. The generated address may or may not be translated. Translation may comprise a virtual-to-physical mapping. Source operand data may contain an immediate integer value included within an instruction. In the example of the load instruction in line 1 of the table 100, the load instruction has an integer value of 8 as an immediate source operand. Another example of source operand data includes data stored in a register by the time execution of the instruction begins. An identifier (ID) within the instruction identifies the register.
[0019] Continuing with the example of the load instruction in line 1 of the table 100, the load instruction has a source register R30 that stores data to be used as source operand data by the time execution of the load instruction begins. An address is generated from an addition operation with the integer 8 and the contents stored in register R30. The generated address may be further translated. The data dependencies between load instructions are highlighted in table 100. Table 100 includes 24 lines of code numbered from line 1 to line 24. The lines of code include instructions presented in program order. In the example shown in table 100, the instructions include load, store and arithmetic addition instructions.
[0020] For a given load instruction, the result data may be retrieved from a cache line within a data cache. However, the result data for the given load instruction may already be in a processor and not need to be retrieved from the data cache using a corresponding generated address. For example, the result data may be in an entry in a store queue. The result data may be forwarded from the store queue within the processor to a destination register of the given load instruction. In this case, the result data is not retrieved from the data cache using the corresponding generated address. The forwarding within the processor of the result data may reduce the latency to obtain the result data for the given load instruction.
[0021] Similar to the above case of forwarding result data, the source operand data of the given load instruction may also be forwarded. The forwarding of source operand data may reduce the latency of the given load instruction and increase instruction throughput. The source operand data may be forwarded to a source register used by the given load instruction. The forwarding of the source operand data may occur in place of retrieving the source operand data from a register file. For example, the source operand data may be forwarded from an arithmetic logic unit (ALU) in an execution unit, an entry in the store queue, and so forth.
[0022] Additionally, the source operand data for the given load instruction may be forwarded directly from a cache pipeline stage. In such a case, the forwarding may occur within a load/store unit (LSU) on the processor after the source operand data is read out from a cache line in a cache array of a data cache. The source operand data for the given load instruction may be retrieved from the data cache due to execution an older (in program order) load instruction. Accordingly, the source operand data may be forwarded to the younger given load instruction within the LSU on the processor. Further details are provided later. In these cases, the given load instruction may be speculatively scheduled to issue early. Other conditions described later may also be checked prior to scheduling the given load instruction early. A predictor may be used to both speculate when data forwarding may be used and to select which source supplies the forwarded data.
[0023] In table 100, line 1 includes a load instruction with a source register denoted as R30. As described earlier, an address is generated from the addition operation using the integer 8 and the contents stored in register R30. The generated address may be additionally translated. If data forwarding is not used to obtain the result data, the contents of memory located at this generated address is retrieved from the data cache. Afterward, the retrieved contents of memory, which also may be referred to as the result data, are sent to the destination register. The load instruction in line 1 has a destination register denoted as R13. In some embodiments, each of the registers R13 and R30 are included in a register file.
[0024] Lines 2 and 3 in table 100 include an addition instruction and a store instruction, respectively. Each of these instructions is dependent on the load instruction in line 1. Therefore, the instructions in lines 2 and 3 may not be scheduled to issue until the result data is at least retrieved from the data cache and placed in an identified destination register within a register file and/or a reservation station.
[0025] The addition instruction in line 2 produces result data that is stored in the destination register R19 in the register file. This result data from the addition instruction is stored in the destination register R19. The result data produced by the addition instruction is also sent to memory for storage by the store instruction in line 3. The load instruction in line 4 utilizes the result data produced by the addition instruction in line 2 as source operand data. Therefore, a corresponding entry in a reservation station for the load instruction in line 4 may receive the result data forwarded from an arithmetic logic unit (ALU). This result data is to be used as source operand data by the load instruction in line 4. The load instruction in line 4 receives source operand data that is in the processor. The latency of the load instruction in line 4 may be reduced due to using forwarded data from the ALU rather than reading data from the register file.
[0026] Table 100 illustrates from where the source operand data is sourced for address generation for load instructions. For example, the load instruction in line 7 uses for address generation the data to be stored in the source register denoted as R2. This data is produced by the load instruction in line 4. The producers of source operand data for load instructions are illustrated in table 100, such as in lines 1, 4, 7, 10, 13, 16, 19 and 22-24.
[0027] Moving to line 19 in table 100, the producer of the source operand data stored in register R7 for the load instruction at line 19 is an older (in program order) load instruction at line 16. The older load instruction at line 16 utilizes register R7 as a destination register. The result data for the older load instruction at line 16 is retrieved from the data cache at the location indicated by “8(R3)”. The address for the load instruction in line 16 is generated from the addition operation between the integer 8 and the data stored in source register R3. In some embodiments, the generated address is translated. The result data stored in a location in the data cache identified by the generated address is retrieved. This result data may be sent to a register file and stored in the register R7 in the register file. Additionally, this result data may be stored in a corresponding entry in a reservation station.
[0028] After the above steps, the load instruction at line 19 may be issued and the result data may be sent to an adder to generate an address for the load instruction at line 19. The adder may be located in an ALU within an integer execution unit. Alternatively, the adder may be located within the LSU. The latency for obtaining and using the result data to be stored in the register R7 may incur an appreciable delay. Long transmission lines, repeater buffers, and staging storage elements may be used to transport the result data from the data cache to the register file. Forwarding the result data to the corresponding entry in the reservation station may reduce the latency. However, the on-die real estate layout may still appreciably affect the latency.
[0029] Continuing with the above example, the result data produced by the load instruction at line 16 may be sent from read out storage elements in the data cache directly to an adder. The adder may be used to generate an address for the load instruction at line 19 by adding the integer 4 to the data stored in the read out storage elements. If the adder is included within the LSU, then this type of forwarding occurs within the LSU, rather than across the die of the processor. The load-to-load latency may be appreciably reduced. Accordingly, the load instruction at line 19 may be scheduled to issue early. For example, in some processor designs, the load-to-load latency may be 4 clock cycles. However, the load-to-load latency may be 3 or less clock cycles when the result data produced by the older load instruction is from a data cache hit and the result data is forwarded within the LSU to the younger, dependent load instruction.
[0030] Similar to the above example regarding the load instruction at line 19, the younger dependent load instructions at lines 22-24 in table 100 may be scheduled early. The load instructions at lines 19 and 22-24 may be scheduled to issue prior to the result data is stored in a corresponding entry in a reservation station or a scheduler. The load instructions may be scheduled prior to the result data being available within the LSU. For each of these load instructions, the result data produced by an older load instruction may be forwarded within the LSU. This local forwarding may appreciably reduce the load-to-load latency.
[0031] Each of the load instructions at lines 19 and 22-24 satisfy conditions for being scheduled to issue early and reduce the load-to-load latency. For example, each of these load instructions is dependent on an older load instruction, rather than an arithmetic operation, a store operation or other operation. Additionally, another condition may be a corresponding older load instruction receives or is scheduled to receive the result data from a data cache hit, rather than from the store queue. Determining the conditions are satisfied for early scheduling of load instructions may utilize preexisting logic in the processor. Further details are provided later. The load instructions at lines 19 and 22-24 may correspond to a traversal of one or more linked lists within a software application. Reducing the load-to-load latency may improve processor performance for processing the instructions of the application.
[0032] The load instructions at lines 1, 4, 7, 10, 13 and 16 do not satisfy the conditions described above. Accordingly, these load instructions are not scheduled to issue early as described above. The load instructions at lines 1, 4 and 10 are not dependent on an older load instruction. The source operand data for the load instructions at lines 7, 13 and 16 are dependent on older load instructions that receive or are scheduled to receive result data from a source other than a data cache hit. For example, the source may be the store queue. Next, a description of the components of a processor used to determine the conditions for allowing early scheduling and thus reducing the load-to-load latency are provided.
[0033] Referring to FIG. 2 , a generalized block diagram illustrating one embodiment of a processor 10 is shown. In the illustrated embodiment, the processor 10 includes a fetch control unit 12 , an instruction cache 14 , a decode unit 17 , a mapper 18 , a scheduler 20 , a register file 22 , an execution core 30 , and an interface unit 60 . As is well known in the art, the processor 10 may operate on multiple threads and include multiple cores, where each core includes the components shown in FIG. 2 . A brief description of each of these components is provided here. A description of the execution core 30 including a load-store unit (LSU) 40 used for handling memory accesses is initially described. A description of the remaining components shown in processor 10 follows this description.
[0034] The execution core 30 may include a load-store unit (LSU) 40 for processing memory access operations, such as integer and floating-point load and store instructions and other types of memory reference instructions. The LSU 40 may access a data cache (d-cache) 50 . The d-cache 50 may be a first level of a multi-level memory hierarchy. For example, the d-cache 50 may be a level one (L1) d-cache placed on the die. In some embodiments, the L1 d-cache may be placed within the execution core 30 . In other embodiments, the L1 d-cache may be placed elsewhere in the processor 10 . The d-cache 50 may include a cache controller 52 for receiving memory access requests and indexing the cache array 54 . The cache array 54 may store data determined likely to be used again based on temporal and special locality. The cache array 54 may utilize a direct-mapped, a fully associative, or a set-associative storage arrangement. Both metadata and data that is read out of the cache array 54 may be stored in the read results 56 . The read results 56 may utilize storage elements, such as flip-flops or latches. The LSU 40 may include logic for detecting data cache misses and to responsively request data from the multi-level memory hierarchy. For example, a miss request may go to a lower level of the memory hierarchy, such as at least a L2 data cache.
[0035] The actual computation of addresses for load/store instructions may take place within a computation unit in the execution core 30 , such as in the integer and floating-point (FP) execution units 34 . Although in other embodiments, the LSU 40 may implement dedicated address generation logic. For example, the LSU 40 may include the address generation unit (AGU) 46 . In some embodiments, the LSU 40 may implement an adaptive, history-dependent hardware prefetcher configured to predict and prefetch data that is likely to be used in the future.
[0036] The LSU 40 may include load and store buffers configured to store issued but not-yet-committed load and store instructions for the purposes of coherency snooping and dependency checking for bypassing data. A load queue 44 may hold addresses of not-yet-committed load instructions. In some embodiments, the data corresponding to these addresses may also be stored in the load queue 44 . In other embodiments, the data corresponding to these addresses may be sent on buses to other components on the processor. The data may arrive from the read results 56 in the d-cache 50 or from the store queue 42 . The LSU 40 may include a miss buffer (not shown) configured to store outstanding loads and stores that cannot yet complete, for example due to cache misses.
[0037] A store queue 42 may hold addresses of not-yet-committed store instructions. The data corresponding to these addresses may be stored in the store queue 42 . Alternatively, the corresponding data may be stored in a separate store buffer (not shown). Accessing the store queue 42 and forwarding data from the store queue 42 to a younger dependent load instruction 44 may consume an appreciable amount of time. In particular it may take longer than accessing the d-cache 50 .
[0038] The store queue 42 and the load queue 44 maintain information for in-flight load and store instructions. A load instruction may have corresponding data from an older store instruction bypassed to it. The corresponding data may be stored in the store queue 42 prior to being written into the L1 d-cache. As load instructions enter the LSU 40 , a dependency check may be performed for determining possible data bypass. The dependency check may comprise a content-addressable-memory (CAM) access of the store queue 42 to compare addresses between in-flight load and store instructions. When an address is resolved (generated and possibly translated) for a given load instruction, this address may be used to index the store queue 42 . A match with an address stored in the store queue 42 in addition to a match with predetermined status and age information produces an access hit. A hit indicates data from an older store instruction may be bypassed from the store queue 42 to the load instruction. A corresponding read access of the d-cache 50 may be cancelled. A prediction of the access results may occur in an earlier pipeline stage. For example, a load/store (LS) predictor 19 may maintain prediction information for store-to-load (STL) forwarding.
[0039] The LS predictor 19 may store program counter (PC) address information of load instructions that have been previously found to be dependent on older store instructions. PC address information of the particular older store instruction may also be stored in a corresponding entry in the LS predictor 19 . The LS predictor 19 may additionally store an indication indicating whether a given store instruction with a dependent load instruction has already received result data. Therefore, the LS predictor 19 maintains information for STL forwarding for both cases where the result data has not yet arrived in the store queue 42 for the store instruction and where the result data has already arrived in the store queue 42 for the store instruction. The LS predictor 19 may be used to predict whether a given load instruction receives source data from the L1 d-cache 50 .
[0040] Continuing with the above description, when the PC address of a given load is used to access the LS predictor 19 and the PC address misses in the LS predictor 19 , there may be high confidence that the source operand data for the given load instruction is not from the store queue 42 , but rather from the L1 d-cache 50 . Alternatively, an index may be generated for the given load instruction to use for accessing the LS predictor 19 . For example, a portion of the PC address may be input to a hash function. Other information such as history information may also be input to the hash function to generate the corresponding index. The index generation may be similar to the logic used for branch prediction mechanisms. The given load instruction may be referred to as the producing load instruction. A younger load instruction may be dependent on the given load instruction. This younger, dependent load instruction may be referred to as the consuming load instruction.
[0041] Determining a load-to-load dependency between the producing load instruction and the consuming load instruction may occur prior to or during a register renaming pipeline stage in the processor 10 . For example, the destination register of the producing load instruction may be determined to match the source register of the consuming load instruction. In addition, no intervening instruction between the producing and consuming load instructions modify or store the result data of the producing load instruction. Similarly, predicting the result data for the producing load instruction is from the d-cache 50 rather than from the store queue 42 may occur prior to or during the register renaming pipeline stage in the processor 10 .
[0042] In response to both (i) determining the load-to-load dependency exists between the producing and consuming load instructions and (ii) a corresponding index for the producing instruction does not hit in the LS predictor 19 , thus, predicting the producing load instruction receives its result data from the L1 d-cache 50 , the consuming load instruction may be scheduled to issue from the scheduler 20 to the execution core 30 early prior to the source operand data is available. An LSU-internal forwarding condition may include the step of predicting the result data for the producing load instruction is available directly from the L1 d-cache 50 . This result data for the producing load instruction is the source operand data for the consuming load instruction. The source operand data may be forwarded within the LSU 40 after the L1 d-cache hit for the producing load instruction. For example, the result data for the producing instruction may be sent from the read results 56 in the d-cache 50 to the AGU 46 . The AGU 46 may use the received data for generating an address for the consuming load instruction. The producing and consuming instructions may be used in a pointer chasing scenario, such as a traversal of a linked list.
[0043] If the prediction is wrong, such as there is a L1 d-cache miss for the producing load instruction or the producing load instruction actually produces a CAM match hit in the store queue 42 , then the consuming load instruction may be replayed. One or more instructions younger than the producing instruction may also be replayed. Depending on the replay logic, either all younger instructions are replayed or only younger instructions dependent on the producing load instruction are replayed.
[0044] In some embodiments, a further qualifying condition for issuing the consuming load instruction early may be a count of replays is below a given threshold. Either the scheduler 20 , the LSU 40 , or logic in the execution core 30 may maintain a respective count of replays for one or more detected consuming load instructions. The count may be for consecutive replays and reset when a prediction is correct. Alternatively, the count may be incremented for each replay and decremented for each correct prediction. Further, the count may be maintained over a given time period and the count is reset at the end of each time period. In response to logic determining a respective count has reached a given threshold, logic in the processor 10 may block an early issue of a corresponding consuming load instruction.
[0045] A further description of the remaining components in processor 10 now follows. In some embodiments, processor 10 may implement an address translation scheme in which one or more virtual address spaces are made visible to executing software. Memory accesses within the virtual address space are translated to a physical address space corresponding to the actual physical memory available to the system, for example using a set of page tables, segments, or other virtual memory translation schemes. In embodiments that employ address translation, each of the data caches and the instruction cache 14 may be partially or completely addressed using physical address bits rather than virtual address bits. For example, the caches may use virtual address bits for cache indexing and physical address bits for cache tags.
[0046] In order to avoid the cost of performing a full memory translation when performing a cache access, processor 10 may store a set of recent and/or frequently used virtual-to-physical address translations in a translation lookaside buffer (TLB), such as the data TLB (DTLB) 32 and the instruction TLB (ITLB) 16 . During operation, each of the ITLB 16 and the DTLB 32 (which may be implemented as a cache, as a content addressable memory (CAM), or using any other suitable circuit structure) may receive virtual address information and determine whether a valid translation is present. If so, each of the ITLB 16 and the DTLB 32 may provide the corresponding physical address bits to a corresponding cache. It is noted that although ITLB 16 and DTLB 32 may perform similar functions, in various embodiments they may be implemented differently. For example, they may store different numbers of translations and/or different translation information.
[0047] Generally, each of the data caches, such as d-cache 50 , and the instruction cache (i-cache) 14 may store one or more lines, each of which is a copy of data stored at a corresponding address in the system memory. As used herein, a “line” is a set of bytes stored in contiguous memory locations, which are treated as a unit for coherency purposes. As used herein, the terms “cache block”, “block”, “cache line”, and “line” are interchangeable. In some embodiments, a cache line may also be the unit of allocation and deallocation in a cache. In some embodiments, each of the caches 14 and 26 may return one or more additional cache lines not yet requested when returning a first cache line that is requested. The instructions or data returned from this prefetch mechanism may be buffered for subsequent use.
[0048] The execution core 30 may include several computation units that perform arithmetic operations, bitwise logic operations, and detection of branch mispredictions. The execution core 30 may calculate and compare target addresses for branch operations, and generate addresses for memory access operations. These computation units are grouped within the integer and FP execution units 34 and not explicitly shown for ease of illustration. The execution core 30 may also be configured to detect various events during execution of ops that may be reported to the scheduler. Branch operations (ops) may be mispredicted, and some load/store ops may be replayed (e.g. for address-based conflicts of data being written/read). Various exceptions may be detected (e.g. protection exceptions for memory accesses or for privileged instructions being executed in non-privileged mode, exceptions for no address translation, etc.). The exceptions may cause a corresponding exception handling routine to be executed.
[0049] The fetch control unit 12 is coupled to provide a program counter address (PC) for fetching from the instruction cache 14 . The instruction cache 14 is coupled to provide instructions (with PCs) to the decode unit 17 , which is coupled to provide decoded instruction operations (ops, again with PCs) to the mapper 18 . Relatively simple op generations (e.g. one or two ops per instruction) may be handled in hardware while more extensive op generations (e.g. more than three ops for an instruction) may be handled in micro-code. In addition, the fetch control unit 12 may handle branch prediction algorithms.
[0050] The mapper 18 is coupled to provide ops, a scheduler number (SCH#), source operand numbers (SO#s), one or more dependency vectors, and PCs to the scheduler 20 . The mapper 18 may implement register renaming to map source register addresses from the ops to the source operand numbers (SO#s) identifying the renamed source registers. Additionally, the mapper 18 may be configured to assign a scheduler entry to store each op, identified by the SCH#. In one embodiment, the SCH# may also be configured to identify the rename register assigned to the destination of the op. In other embodiments, the mapper 18 may be configured to assign a separate destination register number. The mapper 18 may be configured to generate dependency vectors for the op. The dependency vectors may identify the ops on which a given op is dependent. The mapper 18 may provide the ops, along with SCH#, SO#s, PCs, and dependency vectors for each op to the scheduler 20 .
[0051] The scheduler 20 is coupled to receive replay, mispredict, and exception indications from the execution core 30 . In addition, the scheduler 20 may be coupled to provide a redirect indication and redirect PC to the fetch control unit 12 and the mapper 18 , provide ops for execution to the execution core 30 and is coupled to the register file 22 . The register file 22 is coupled to provide operands to the execution core 30 , and is coupled to receive results to be written from the execution core 30 . The register file 22 may generally include any set of registers usable to store operands and results of ops executed in the processor 10 . In other embodiments, processor 10 may utilize reservation stations as part of a scheduling mechanism. For example, reservation stations may be utilized on a per execution unit basis. These and other embodiments are possible and are contemplated.
[0052] The execution core 30 is coupled to the interface unit 60 , which is further coupled to an external interface of the processor 10 . The external interface may include any type of interconnect (e.g. bus, packet, etc.). The external interface may be an on-chip interconnect, if the processor 10 is integrated with one or more other components (e.g. a system on a chip configuration). The external interface may be on off-chip interconnect to external circuitry, if the processor 10 is not integrated with other components. It is contemplated that processor 10 may implement any suitable instruction set architecture (ISA), such as, e.g., the ARM™, PowerPC™, or x86 ISAs, or combinations thereof.
[0053] Referring now to FIG. 3 , a generalized flow diagram of one embodiment of a method 300 for efficient scheduling of speculative load instructions is shown. The components embodied in processor 10 may generally operate in accordance with method 300 . For purposes of discussion, the steps in this embodiment are shown in sequential order. However, in other embodiments some steps may occur in a different order than shown, some steps may be performed concurrently, some steps may be combined with other steps, and some steps may be absent.
[0054] In block 302 , a processor may be processing instructions of one or more software applications. The processor fetches instructions of one or more software applications. In various embodiments, these fetched instructions may be decoded, renamed and allocated in a scheduler where they are later issued to an execution core. The processing may occur concurrently for one or more threads.
[0055] For a given thread, if the processor detects a load instruction (conditional block 304 ), then in 306 , logic in the processor determines whether the detected load is dependent on an older load instruction. For example, a decode unit and a mapper in the processor may perform this determination. In block 308 , logic in the processor predicts whether the result data of the older load instruction, which may also be referred to as the producing load instruction, is sourced from the data cache (i.e., the result data is predicted to be resident in the data cache). For example, a hash function may receive at least a portion of the PC address for the producing load instruction and generate an index. The index may be used to access a load-store (LS) predictor used to find store-to-load (STL) forwarding cases. If the index does not hit in the LS predictor, then in one embodiment it may be assumed that the result data for the producing load instruction is from the data cache.
[0056] In some embodiments, the steps in blocks 306 and 308 may occur in the same pipeline stage. The window of instructions to simultaneously process in a clock cycle may include the producing and the consuming load instructions. For a traversal of a linked list, the producing and consuming load instructions may be located near one another in the compiled computer program. If either one of the conditions determined in blocks 304 and 306 is not satisfied, then processing may resume with block 302 . In conditional block 308 , if the result data for the older load is not predicted to be in the data cache, then in block 312 , the detected load instruction is not issued early in order to receive source operand data early from the data cache. Rather, the detected load instruction may be issued when the source operand data is ready and received. For example, the source operand data may be forwarded from the store queue or an ALU component to an entry in the scheduler or a reservation station. Additionally, the source operand data is written to a register file. If forwarding is not used, the source operand data may be read from the register file for the detected load instruction. Alternatively, if in block 308 the result data for the older load is predicted to be in the data cache, then in block 314 , the detected load instruction may be issued early (i.e., prior to the source operand data being available). The early issue may reduce the load-to-load latency. The detected load instruction may receive the source operand data in the LSU.
[0057] Turning now to FIG. 4 , a generalized flow diagram of one embodiment of a method 400 for executing early scheduled speculative load instructions is shown. The components embodied in processor 10 may generally operate in accordance with method 400 . For purposes of discussion, the steps in this embodiment are shown in sequential order. However, in other embodiments some steps may occur in a different order than shown, some steps may be performed concurrently, some steps may be combined with other steps, and some steps may be absent.
[0058] In block 402 , a processor may be processing instructions of one or more software applications. In block 404 , the processor may issue a load instruction early based on predicting that the source operand data, which may also be referred to as the dependent data, will be sourced locally within the LSU from the data cache. The prediction may be based on conditions, such as the conditions described for method 300 . In block 406 , the prediction to issue the load instruction early may be resolved. For example, the early issued load instruction may be the consuming load instruction. Each of the hit/miss status of an access of the L1 data cache and an access of the store queue for the older producing load instruction may be resolved.
[0059] A misspeculation of the scheduling of the producing load instruction may be due to the instruction hitting in the store queue or some other condition (such as an alignment restriction) making the early forwarding from the d-cache impossible. If a misspeculation is detected (conditional block 408 ), then in block 410 , one or more instructions younger (in program order) than the producing load instruction are replayed. The consuming load instruction itself may or may not need to be replayed. In some embodiments, the dependency information may be used to select which younger instructions to replay. The dependency information may be used to cancel the younger dependent instructions in various locations throughout processor. In other embodiments, all younger instructions are replayed. The replay may also reset stored values in the scheduler, such as deasserting picked or issued status information.
[0060] In various embodiments, program instructions of a software application may be used to implement the methods and/or mechanisms previously described. The program instructions may describe the behavior of hardware in a high-level programming language, such as C. Alternatively, a hardware design language (HDL) may be used, such as Verilog. The program instructions may be stored on a computer readable storage medium. Numerous types of storage media are available. The storage medium may be accessible by a computer during use to provide the program instructions and accompanying data to the computer for program execution. In some embodiments, a synthesis tool reads the program instructions in order to produce a netlist comprising a list of gates from a synthesis library.
[0061] Although the embodiments above have been described in considerable detail, numerous variations and modifications will become apparent to those skilled in the art once the above disclosure is fully appreciated. It is intended that the following claims be interpreted to embrace all such variations and modifications. | A system and method for efficient scheduling of dependent load instructions. A processor includes both an execution core and a scheduler that issues instructions to the execution core. The execution core includes a load-store unit (LSU). The scheduler determines a first condition is satisfied, wherein the first condition comprises result data for a first load instruction is predicted eligible for LSU-internal forwarding. The scheduler determines a second condition is satisfied, wherein the second condition comprises a second load instruction younger in program order than the first load instruction is dependent on the first load instruction. In response to each of the first condition and the second condition being satisfied, the scheduler can issue the second load instruction earlier than it otherwise would. The LSU internally forwards the received result data from the first load instruction to address generation logic for the second load instruction. | 6 |
CLAIM OF PRIORITY
[0001] This application is a continuation of U.S. Non-Provisional patent application Ser. No. 14/021,993 filed Sep. 9, 2013 and entitled ASYNCHRONOUS HYBRID ARQ PROCESS INDICATION IN A MIMO WIRELESS COMMUNICATION SYSTEM, now U.S. Pat. No. 9,071,434, which is a continuation of U.S. Non-Provisional patent application Ser. No. 12/222,113 filed Aug. 1, 2008 and entitled ASYNCHRONOUS HYBRID ARQ PROCESS INDICATION IN A MIMO WIRELESS COMMUNICATION SYSTEM, now U.S. Pat. No. 8,553,624, and claims priority to U.S. Provisional Patent Application No. 60/960,709 filed Oct. 10, 2007 and entitled ASYNCHRONOUS HYBRID ARQ PROCESS INDICATION IN A MIMO WIRELESS COMMUNICATION SYSTEM. The content of the above-identified documents is incorporated herein by reference.
BACKGROUND
[0002] 1. Field of the Disclosure
[0003] The present disclosure relates to transmitting Asynchronous Hybrid Automatic Repeat request (ARQ) process identities in a wireless communication system.
[0004] 2. Description of the Related Art
[0005] During data transmission, especially wireless data transmission, error inevitably occurs to decrease the quality of the transmitted data. Therefore, the data is retransmitted in order to correct the error.
[0006] Automatic Repeat-reQuest (ARQ) is an error control method for data transmission which makes use of acknowledgements and timeouts to achieve reliable data transmission. An acknowledgement is a message sent by the receiver to the transmitter to indicate that it has correctly received a data frame.
[0007] Usually, when the transmitter does not receive the acknowledgement before the timeout occurs (i.e., within a reasonable amount of time after sending the data frame), the transmitter retransmits the frame until the data within the frame is either correctly received or the error persists beyond a predetermined number of re-transmissions.
[0008] Hybrid ARQ (HARQ) is a variation of the ARQ error control method, which gives better performance than the ordinary ARQ scheme, particularly over wireless channels, at the cost of increased implementation complexity. One version of HARQ is described in the IEEE 802.16e standard.
[0009] The HARQ protocol can be further classified into a synchronous HARQ protocol and an asynchronous HARQ protocol. In the synchronous HARQ protocol, the retransmissions happen at fixed time intervals and control information only needs to be transmitted along with a first subpacket transmission. The drawback of synchronous HARQ, however, is that the retransmission subpackets cannot be scheduled at preferable channel conditions because the timing of the retransmission is predetermined. Also, the modulation, coding and resource format cannot be adapted at the time of retransmission according to the prevailing channel conditions at the time of retransmission.
[0010] In the asynchronous HARQ protocol, the retransmission timing, modulation, coding and resource format can be adapted according to the prevailing channel and resource conditions at the time of retransmission. The control information, however, needs to be sent along with all the subpackets. The control information transmission along with each subpacket allows adjusting the transmission timing, modulation, coding and resources allocated.
[0011] In the 3rd Generation Partnership Project (3GPP) Long Term Evolution (LTE) systems, a maximum of two codewords are used for transmission of two, three or four MIMO layers. In addition, an HARQ process identity is used to indicate the ID of the channel in an N-channel HARQ system. For example, a 3-bit process ID allows simultaneous operation on 8 SAW channels.
[0012] When two subpackets from two respectively corresponding codewords are transmitted using the HARQ transmission scheme, the transmission rank may change from 2 to 1 at time of retransmission. If both subpackets used a process ID of 0 (PID=0) at the first transmission in rank-2, only a single codeword can be retransmitted in rank-1. This is because a single subpacket under a single PID can be retransmitted in rank-1. The second codeword transmission has to start from the beginning at a later time. This results in loss of the previously transmitted subpacket in rank-2.
[0013] When two subpackets from two respectively corresponding codewords are transmitted using the HARQ transmission scheme, the transmission rank may also change from 1 to 2 at time of retransmission. If a first subpacket uses a process ID of 0, while a second subpacket uses a process ID of 1 at the first transmission in rank-1, the two codewords are transmitted in rank-1 in two subframes because a single codeword can be transmitted in rank-1 in a given subframe. We note that the retransmissions for the two codewords can be performed in rank-2 because the two codewords are transmitted on different hybrid ARQ processes.
SUMMARY
[0014] It is therefore an object of the present disclosure to provide an improved method and apparatus for wireless communication.
[0015] It is another object of the present disclosure to provide an improved method and apparatus for efficiently transmitting Hybrid Automatic Repeat-reQuest (HARQ) process identities.
[0016] According to one aspect of the present disclosure, a linking scheme is established between at least two sets of process identities of two respective corresponding codewords. When a first process identity is selected from among a first set of process identities of a first codeword, a second process identity may be derived in dependence upon the first process identity and the established linking scheme. Finally, a first packet from the first codeword is transmitted using a first transmission channel indicated by the first process identity, and a second packet is transmitted from the second codeword using a second transmission channel indicated by the second process identity. In addition, a control message including only the first process identity is transmitted.
[0017] The control message may also include a codeword to layer mapping field indicating the mapping for the codewords to transmission layers.
[0018] The first packet and the second packet may be transmitted on different frequency subbands.
[0019] According to another aspect of the present disclosure, a linking scheme is established between a certain set of process identity fields and at least two sets of process identities of two respective corresponding codewords. When a process identity field is selected from among the certain set of process identity fields, a first process identity and a second process identity may be derived in dependence upon the selected process identity field and the established linking scheme. Finally, a first packet from the first codeword is transmitted using a first transmission channel indicated by the first process identity, and a second packet is transmitted from the second codeword using a second transmission channel indicated by the second process identity. In addition, a control message including the selected process identity field is transmitted.
[0020] According to still another aspect of the present disclosure, a linking scheme is established between a certain set of process identity fields, a certain set of differential process identities, and at least two sets of process identities of two respective corresponding codewords. Therefore, when a process identity field is selected from among the certain set of process identity fields, and a differential process identity is selected from among the certain set of differential process identities, a first process identity and a second process identity may be derived in dependence upon the selected process identity field, the selected differential process identity and the established linking scheme. Finally, a first packet from the first codeword is transmitted using a first transmission channel indicated by the first process identity, and a second packet is transmitted from the second codeword using a second transmission channel indicated by the second process identity. In addition, a control message including the selected process identity field and the selected differential process identity is transmitted.
BRIEF DESCRIPTION OF THE DRAWINGS
[0021] A more complete appreciation of the subject matter of the present disclosure, and many of the attendant advantages thereof, will be readily apparent as the same becomes better understood by reference to the following detailed description when considered in conjunction with the accompanying drawings in which like reference symbols indicate the same or similar components, wherein:
[0022] FIG. 1 schematically illustrates an Orthogonal Frequency Division Multiplexing (OFDM) transceiver chain;
[0023] FIG. 2 schematically illustrates a scheme for generating subpackets;
[0024] FIG. 3 schematically illustrates an example of Hybrid ARQ scheme in a wireless communication system;
[0025] FIG. 4 schematically illustrates a synchronous Hybrid ARQ scheme;
[0026] FIG. 5 schematically illustrates an asynchronous Hybrid ARQ scheme;
[0027] FIG. 6 schematically illustrates a Multiple Input Multiple Output (MIMO) transceiver chain;
[0028] FIG. 7 schematically illustrates a Single-code word MIMO scheme;
[0029] FIG. 8 schematically illustrates a Multi-code word MIMO scheme;
[0030] FIG. 9 schematically illustrates Multi-code word MIMO scheme for 2-layers transmission in the 3GPP LTE system;
[0031] FIG. 10 schematically illustrates Multi-code word MIMO scheme for 3-layers transmission in the 3GPP LTE system;
[0032] FIG. 11 schematically illustrates Multi-code word MIMO scheme for 4-layers transmission in the 3GPP LTE system;
[0033] FIG. 12 schematically illustrates an 8-channel Asynchronous Hybrid ARQ scheme;
[0034] FIG. 13 schematically illustrates an example of subpackets from two codewords;
[0035] FIG. 14 schematically illustrates an example of HARQ retransmission when rank changes from 2 to 1 at the time of retransmissions;
[0036] FIG. 15 schematically illustrates an example of HARQ retransmission when rank changes from 1 to 2 at time of retransmissions;
[0037] FIG. 16 schematically illustrates an example of HARQ retransmissions for the case when rank changes from 2 to 1 at time of retransmissions as a first embodiment according to the principles of the present disclosure;
[0038] FIG. 17 schematically illustrates an example of HARQ retransmissions for the case when rank changes from 1 to 2 at time of retransmissions as a second embodiment according to the principles of the present disclosure;
[0039] FIG. 18 schematically illustrates an example of HARQ retransmissions for the case when rank changes from 1 to 2 at time of retransmissions as a third embodiment according to the principles of the present disclosure;
[0040] FIG. 19 schematically illustrates an example of HARQ retransmissions for the case when rank changes from 1 to 2 at time of retransmissions as another embodiment according to the principles of the present disclosure;
[0041] FIG. 20 schematically illustrates an example of HARQ retransmissions for the case when rank changes between rank-1 and rank-2 as still another embodiment according to the principles of the present disclosure; and
[0042] FIG. 21 schematically illustrates an example of HARQ retransmissions on different MIMO layers and different OFDM subbands when MIMO rank changes between rank-1 and rank-2 as a further embodiment according to the principles of the present disclosure.
DETAILED DESCRIPTION
[0043] FIG. 1 illustrates an Orthogonal Frequency Division Multiplexing (OFDM) transceiver chain. In a communication system using OFDM technology, at transmitter chain 110 , control signals or data 111 is modulated by modulator 112 and is serial-to-parallel converted by Serial/Parallel (S/P) converter 113 . Inverse Fast Fourier Transform (IFFT) unit 114 is used to transfer the signal from frequency domain to time domain. Cyclic prefix (CP) or zero prefix (ZP) is added to each OFDM symbol by CP insertion unit 116 to avoid or mitigate the impact due to multipath fading. Consequently, the signal is transmitted by transmitter (Tx) front end processing unit 117 , such as an antenna (not shown), or alternatively, by fixed wire or cable. At receiver chain 120 , assuming perfect time and frequency synchronization are achieved, the signal received by receiver (Rx) front end processing unit 121 is processed by CP removal unit 122 . Fast Fourier Transform (FFT) unit 124 transfers the received signal from time domain to frequency domain for further processing.
[0044] The total bandwidth in an OFDM system is divided into narrowband frequency units called subcarriers. The number of subcarriers is equal to the FFT/IFFT size N used in the system. In general, the number of subcarriers used for data is less than N because some subcarriers at the edge of the frequency spectrum are reserved as guard subcarriers. In general, no information is transmitted on guard subcarriers.
[0045] Hybrid Automatic Repeat request (ARQ) is a retransmission scheme whereby a transmitter sends redundant coded information (i.e., subpackets) in small increments. As shown in FIG. 5 , in transmitter 130 , an information packet P is first input into channel coder 131 to perform channel coding. The resulted coded bit stream is input into subpacket generator 132 to break into smaller units, i.e., subpackets SP 1 , SP 2 , SP 3 and SP 4 . The hybrid ARQ retransmissions can either contain redundant symbols or coded bits which are different than the previous transmission(s) or copies of the same symbols or coded bits. The scheme which retransmits copies of the same information is referred to as chase combining. In case of Chase combining, the subpackets SP 1 , SP 2 , SP 3 and SP 4 as shown in FIG. 4 are all identical. The scheme where retransmitted symbols or coded bits are different than the previous transmission is generally referred to as an incremental redundancy scheme.
[0046] An example of Hybrid ARQ protocol is shown in FIG. 3 . After receiving the first subpacket SP 1 from transmitter 130 , receiver 140 tries to decode the received information packet. In case of unsuccessful decoding, receiver 140 stores SP 1 and sends a Negative Acknowledgement (NACK) signal to transmitter 130 . After receiving the NACK signal, transmitter 130 transmits the second subpacket SP 2 . After receiving the second subpacket SP 2 , receiver 140 combines SP 2 with the previously received subpacket SP 1 , and tries to jointly decode the combined information packet. At any point, if the information packet is successfully decoded by indication of a successful Cyclic Redundancy Check (CRC) check, for example, receiver 140 sends an ACK signal to transmitter 130 . In the example of FIG. 3 , the information packet is successfully decoded after receiving and combining three subpackets, SP 1 , SP 2 and SP 3 . The ARQ protocol shown in FIG. 3 is generally referred to as stop-and-wait protocol because the transmitter waits for the ACK/NACK signal before sending the next subpacket. After receiving the ACK signal, the transmitter can move on to transmit a new information packet to the same or a different user.
[0047] An example of N-channel stop-and-wait (SAW) synchronous Hybrid ARQ (HARQ) protocol is shown in FIG. 4 . In the example of FIG. 4 , N is assumed to equal to 4. In case of a synchronous HARQ protocol, the retransmissions happen at fixed time intervals. With N=4, if the first subpacket is transmitted in time slot 1 , the retransmissions of the first subpacket can only happen in slots 5 , 9 and 13 . The number of processes is determined by the time required for ACK/NACK feedback. When the transmitter is waiting for feedback on one HARQ process, the transmitter can transmit another data packet, such as a second subpacket. In case of N-channel stop-and-wait (SAW), N parallel information packets can be transmitted via N SAW channels, with each of the N SAW channels carrying one packet. One of the benefits of the synchronous HARQ protocol is that the control information only needs to be transmitted along with the first subpacket transmission because the timing of the retransmissions is predetermined. The drawback of synchronous HARQ, however, is that the retransmission subpackets cannot be scheduled at preferable channel conditions because the timing of the retransmission is predetermined. Also, the modulation, coding and resource format cannot be adapted at the time of retransmission according to the prevailing channel conditions at the time of retransmission.
[0048] An example of N-channel stop-and-wait (SAW) asynchronous Hybrid ARQ (HARQ) protocol is shown in FIG. 5 . In case of asynchronous HARQ, the retransmission timing, modulation, coding and resource format can be adapted according to the prevailing channel and resource conditions at the time of retransmission. The control information, however, needs to be sent along with all the subpackets as shown in FIG. 5 . The control information transmission along with each subpacket allows adjusting the transmission timing, modulation, coding and resources allocated.
[0049] Multiple Input Multiple Output (MIMO) schemes use multiple transmission antennas and multiple receive antennas to improve the capacity and reliability of a wireless communication channel. A MIMO system promises linear increase in capacity with K where K is the minimum of number of transmit (M) and receive antennas (N), i.e. K=min(M,N). A simplified example of a 4×4 MIMO system is shown in FIG. 6 . In this example, four different data streams are transmitted separately from four transmission antennas. The transmitted signals are received at four receive antennas. Some form of spatial signal processing is performed on ii the received signals in order to recover the four data streams. An example of spatial signal processing is vertical Bell Laboratories Layered Space-Time (V-BLAST) which uses the successive interference cancellation principle to recover the transmitted data streams. Other variants of MIMO schemes include schemes that perform some kind of space-time coding across the transmission antennas (e.g., diagonal Bell Laboratories Layered Space-Time (D-BLAST)) and also beamforming schemes such as Spatial Division multiple Access (SDMA).
[0050] An example of single-code word MIMO scheme is given in FIG. 3 . In case of single-code word MIMO transmission, a cyclic redundancy check (CRC) is added to a single information block and then coding, for example, using turbo codes and low-density parity check (LDPC) code, and modulation, for example, by quadrature phase-shift keying (QPSK) modulation scheme, are performed. The coded and modulated symbols are then demultiplexed for transmission over multiple antennas.
[0051] In case of multiple codeword MIMO transmission, shown in FIG. 4 , the information block is de-multiplexed into smaller information blocks. Individual CRCs are attached to these smaller information blocks and then separate coding and modulation is performed on these smaller blocks. After modulation, these smaller blocks are respectively demultiplexed into even smaller blocks and then transmitted through corresponding antennas. It should be noted that in case of multi-code word MIMO transmissions, different modulation and coding can be used on each of the individual streams, and thus resulting in a so-called Per Antenna Rate Control (PARC) scheme. Also, multi-code word transmission allows for more efficient post-decoding interference cancellation because a CRC check can be performed on each of the code words before the code word is cancelled from the overall signal. In this way, only correctly received code words are cancelled, and thus avoiding any interference propagation in the cancellation process.
[0052] In the 3rd Generation Partnership Project (3GPP) Long Term Evolution (LTE) systems, a maximum of two codewords are used for transmission of two, three or four MIMO layers. As shown in FIG. 9 , for rank-2 or two layers transmission, codeword-1 (CW 1 ) is transmitted from Layer-0 while CW 2 is transmitted from Layer-1. For rank-3 or three layers transmission as shown in FIG. 10 , codeword-1 (CW 1 ) is transmitted from Layer-0 while CW 2 is transmitted from Layer-1 and Layer-2. For rank-4 or four layers transmission as shown in FIG. 11 , codeword-1 (CW 1 ) is transmitted from Layer-0 and Layer-1 while CW 2 is transmitted from Layer-2 and Layer-3.
[0053] In the 3GPP LTE system, a 3-bit HARQ process identity (ID) is used. The process ID refers to the ID of the channel in the N-channel stop-and-wait HARQ. The 3-bit process ID allows simultaneous operation on eight SAW channels. In the example of FIG. 12 , the initial subpacket SP 1 is transmitted in subframe#0 on process with process ID 0 (PID=0). The retransmissions SP 2 and SP3 are performed in subframe#7 and subnframe#15. With 8 HARQ processes, the minimum time between retransmissions is 8 subframes.
[0054] An example of subpackets from two codewords is shown in FIG. 13 . We assume that each codeword consists of four subpackets. The subpackets are referred as redundancy versions (RV) in the context of circular buffer rate matching used in the 3GPP LTE system. The subpackets or RVs are transmitted in response to ACK/NACK feedback from the receiver.
[0055] An example of HARQ retransmission of the two codewords shown in FIG. 13 when rank changes from 2 to 1 at time of retransmission is shown in FIG. 14 . We assume that the transmission of the subpackets from both codewords fails on first attempt. As the rank changes to 1 at time of subpacket retransmission, only a single codeword can be retransmitted in rank-1. This is because both subpackets used the same process number that is process ID 0 (PID=0) and a single subpacket under a single PID can be retransmitted in rank-1. The second codeword transmission has to start from the beginning by transmission of subpacket SP 21 at a later time. This results in loss of the previously transmitted subpacket SP 21 in rank-2.
[0056] The possible Hybrid ARQ feedback message formats are listed in Table 1.
[0000]
TABLE 1
Hybrid ARQ ACK/NACK feedback
HARQ
Feedback
CW1
CW2
ACK(0)
Negatively Acknowledged
NA
ACK(1)
Positively Acknowledged
NA
ACK(0, 0)
Negatively Acknowledged
Negatively Acknowledged
ACK(0, 1)
Negatively Acknowledged
Positively Acknowledged
ACK(1, 0)
Positively Acknowledged
Negatively Acknowledged
ACK(1, 1)
Positively Acknowledged
Positively Acknowledged
[0057] An example of HARQ retransmission when rank changes from 1 to 2 at time of retransmissions is shown in FIG. 15 . Two codewords are transmitted in rank-1 in two subframes because a single codeword can be transmitted in rank-1 in a given subframe. We assume that both the codewords requires retransmission. We further assume that the MIMO rank changes to a rank greater than 1 enabling transmission of two codewords. We note that the retransmissions for the two codewords cannot be performed in rank-2 because the two codewords neet to be transmitted on different hybrid ARQ processes.
[0058] In the current disclosure, we describe a scheme that allows scheduling retransmissions when rank changes at the time of retransmissions.
[0059] In a first embodiment according to the principles of the current disclosure, in a rank-2 transmission, the process ID of the second CW is linked to the process ID of the first codeword. This requires indication of only CW 1 PID in the control message during the rank-2 transmission while PID for CW 2 is derived from CW 1 as shown in Table 2. This scheme allows for HARQ retransmissions when the MIMO rank changes from 2 to 1 as shown in FIG. 16 . As shown in FIG. 16 , the first transmission is a rank-2 transmission. In the first transmission, the PID 1 for CW 1 is explicitly transmitted, while the PID 2 for CW 2 is derived from the PID 1 based on Table 2. In the second transmission (retransmission), the rank changed from rank-2 to rank-1. In this rank-1 transmission, there is no link between PID 1 for CW 1 and PID 2 for CW 2 , and therefore both of the PID 1 and PID 2 are explicitly transmitted in rank-1. Table 2 is only for rank-2 transmission, instead of rank-1 transmission. Note the number of available process indications in rank-1 is sixteen (16), while the number of available process indications in rank-2 is eight (8). This HARQ retransmission requires that, however, the PID field in rank-1 is 1-bit longer than the PID field in-rank-2. For example, if 3-bits PID representing CW 1 PIDs from 0 to 7 (with CW 2 PIDs 8 - 15 implicitly derived) is used in rank-2, then a 4-bit PID representing PIDs from 0-15 is required in rank1.
[0060] In the example of FIG. 16 , subpackets from four codewords are transmitted in two subframes with rank-2 (allows two simultaneous codeword transmission). Note that in FIG. 16 , the linking scheme between PID 3 for CW 3 and PID 4 for CW 4 is the same as the linking scheme between PID 1 and PID 2 . We assume that all the four codewords are negatively acknowledged and requires HARQ retransmissions. Meanwhile, the rank changes to 1 and therefore the subsequent subpackets from the four codewords are transmitted in four subframes with one subpacket transmitted in each subframe. The subpackets can be retransmitted in rank-1 with one subpacket per subframe because the number of hybrid ARQ process IDs (PIDs) is 2 times more in rank-1 than in rank-2 (16 PIDs in rank-1 versus 8 PIDs in rank-2). The principles of the current disclosure can be extended to the case when more than two codewords are transmitted simultaneously using multi-codeword MIMO. For example, when the number of MIMO codewords is four, a 3-bit process ID can be used for the four codewords transmission in rank-4, and the subpackets for these 4 codewords can be transmitted in rank-1 by providing 4 times more PIDs (5-bits PIDS in rank-1), because there are totally thirty-two (32) channels in the HARQ scheme for the four codewords. Similarly, when 4 codewords are transmitted in rank-2 with 2 codewords simultaneously transmitted, the PID size in rank-2 can be 4-bits. In the case of rank-2 transmission, there are two linking schemes for two pairs of codewords. For example, there is a first linking scheme between PID 1 and PID 2 , and there is a second linking scheme between PID 3 and PID 4 .
[0000]
TABLE 2
A scheme linking CW2 PID with CW1 PID
PID field
CW1 process ID
CW2 process ID
000
0
8
001
1
9
010
2
10
011
3
11
100
4
12
101
5
13
110
6
14
111
7
15
[0061] In Table 2, the process ID for CW 2 (PID 2 ) is linked to the process ID for CW 1 (PID 1 ) as below:
[0000] PID2=PID1+8 (1)
[0062] Other functions for Hybrid ARQ PID linking between CW 1 and CW 2 can also be used. Another example is shown in Table 3 below where CW 2 process ID (PID 2 ) is linked to PID 1 as below:
[0000] PID2=16−PID1 (2)
[0000]
TABLE 3
A scheme linking CW2 PID with CW1 PID
PID field
CW1 process ID
CW2 process ID
000
0
15
001
1
14
010
2
13
011
3
12
100
4
11
101
5
10
110
6
9
111
7
8
[0063] In a second embodiment according to the principles of the present disclosure, an example of HARQ retransmissions according to the principles of the current disclosure for the case when rank changes from 1 to 2 at time of retransmissions is shown in FIG. 17 . The process IDs use is assumed to be according to Table 3. We assume four subpackets from four different transport blocks (codewords) are transmitted in rank-1. At the time of retransmission when rank changes to 2, the subpackets transmitted on PID#7 and PID#8 can be scheduled together in rank-2 as allowed by the mapping in Table 3. The subpackets originally transmitted on PID#5 and PID#6 cannot, however, be scheduled together because this combination is not allowed by mapping in Table 3. Note that two process indications in the same row in Table 3 is an allowed combination.
[0064] In a third embodiment according to the principles of the present disclosure, the process IDs for CW 1 and CW 2 are derived from a single 3-bit field as in Table 4. CW 1 uses odd numbers PIDs while CW 2 uses even numbered PIDs. This scheme allows simultaneous scheduling of two subpackets retransmissions from rank-1 to rank-2, when the PIDs of the two subpackets are in the same row in Table 4. As shown in FIG. 18 , PID 1 for CWI (SP 11 ) is 4, and PID 2 for CW 2 (SP 21 ) is 5. PID#4 and PID#5 are in the same-row in Table 4, and hence the retransmissions of the respective corresponding codewords, CW 1 and CW 2 , can be scheduled together when the rank changes from 1 to 2. This scheme does not allow, however, retransmission of subpackets on process IDs when the process IDs are not in the same row. For example, PID#4 and PID#5 are not in the same row in Table 3, and hence subpackets on PID#4 and PID#5 cannot be retransmitted together in rank-2.
[0000]
TABLE 4
CW1 and CW2 PIDs with a single 3-bit PID field
PID field
CW1 process ID
CW2 process ID
000
0
1
001
2
3
010
4
5
011
6
7
100
8
9
101
10
11
110
12
13
111
14
15
[0065] In a fourth embodiment according to the principles of the present disclosure, a full PID field and a differential process ID (DPID) field is used for two codewords transmission. An example with a 1-bit DPID field linking CW 2 PID with CW 1 PID is shown in Table 5. When the DPID field is set to ‘0’, CW 1 PIDs are even numbered while CW 2 PIDs are odd numbered, as given by the following relationship:
[0000] PID2=(PID1+1)mod 16, when DPID=‘0’ (3)
[0066] When DPID field is set to ‘1’, both CW 1 and CW 2 PIDs are even numbered. However, PIDs for CW 2 are shifted by 2, as given by the following relationship:
[0000] PID2=(PID1+2)mod 16, when DPID=‘1’ (4)
[0067] This principle can be further extended by using more than 1-bit for the DPID filed. For example, with 2-bit DPID field, the CW 1 and CW 2 PIDs can be linked as below
[0000] PID2=(PID1+1)mod 16, when DPID=‘00’ (5)
[0000] PID2=(PID1+5)mod 16, when DPID=‘01’ (6)
[0000] PID2=(PID1+9)mod 16, when DPID=‘10’ (7)
[0000] PID2=(PID1+13)mod 16, when DPID=‘11’ (8)
[0068] The larger the DPID field, more flexibility is allowed in hybrid ARQ retransmissions when the MIMO rank changes between original transmission and retransmissions.
[0000]
TABLE 5
CW1 and CW2 PIDs linking by using a single-bit DPID
CW2 process ID
CW2 process ID
PID field
CW1 process ID
(DPIP = ‘0’)
(DPIP = ‘1’)
000
0
1
2
001
2
3
4
010
4
5
6
011
6
7
8
100
8
9
10
101
10
11
12
110
12
13
14
111
14
15
0
[0069] In a fifth embodiment according to the principles of the present disclosure, a 3-bit process ID is used for two codewords transmissions (rank-2 or greater) and a 4-bit process ID is used for one codeword transmission (rank-1). An extra codeword to layer mapping (CLM) bit, however, is used for two codewords transmission. When this bit is set, the bit flips the mapping of codewords to layers as shown in FIG. 19 . When CLM bit is set to ‘0’, PID#6 and PID#7, for example, goes on Layer-1 (CW 1 ) and Layer-2 (CW 2 ) respectively according to Table 4. On the other hand when the CLM bit is set to ‘1’, PID#6 and-PID#7 goes on Layer-2 (CW 2 ) and Layer-1 (CW 1 ) respectively as shown in FIG. 19 . In this way, the total number of bits is the same between single codeword and two codewords transmission, that is 4-bits process ID for rank-1 and 3-bits process ID+1-bit CLM indication for rank-2 and greater.
[0070] In a sixth embodiment according to the principles of the present disclosure, two 4-bits process IDs (total of 8-bits) are used for two codewords transmission while a single 4-bit process ID is used for a single codeword transmission as given in Table 6. This scheme allows for full flexibility in scheduling and pairing subpackets at retransmissions when rank changes such that at sometimes only a single codeword is transmitted while at other times two codewords can be transmitted. We illustrate this flexibility by considering the example shown in FIG. 20 . We assume that the four subpackets transmitted in rank-2 need retransmissions in rank-1. Since a 4-bit PID is available in rank-1, the four codewords can be transmitted in four subframes with each codewords needs its now PID. The subpacket on processes with IDs 0 and 3 fail again and are retransmitted in rank-2 again. Since each codeword has its own 4-bit process ID, the subpackets from these two codewords can be scheduled together in rank-2.
[0000]
TABLE 6
CW1 and CW2 PIDs with 4-bits PID fields
Rank-1
Rank-2
Total bits = 4
Total bits = 8
CW1 process IDs
CW1 process IDs
CW2 process IDs
4-bits indicate PIDs
4-bits indicate PIDs
4-bits indicate PIDs
from 0-15
from 0-15
from 0-15
[0071] In a seventh embodiment according to the principles of the present disclosure shown in FIG. 21 , the retransmissions form the two codewords transmitted on different layers can be scheduled on different frequency subbands in OFDM. Initially four subpackets are transmitted on two layers and two subframes in rank-2. The two of the four subpackets fail and are retransmitted on a single layer in rank-1 on two OFDM subbands. A subband consists of multiple OFDM subcarriers in a single subframe. Two new subpackets, SP 51 and SP 61 are scheduled on two subbands on PIDs 0 and 9 respectively. The retransmission for SP 32 and SP 61 on PIDs 3 and 9 respectively are then retransmitted on two layers in rank-2 in a single subframe. By allowing retransmissions in frequency-domain, two subpackets can be scheduled simultaneously in a single subframe, thus speeding up the retransmissions and lowering the packet transmissions delays. It is also possible to initiate transmission of two subpackets on different subbands as is the case for subpackets SP 51 and SP 61 scheduled on PIDs 0 and 9 respectively. The same ACK/NACK feedback structure as for 2 codeword rank-2 transmission given in Table 1 can be used when two subpackets are scheduled on different subbands. In both cases, a 2-bit ACK/NACK for the two codewords is needed.
[0072] The above embodiments of the principles of the present disclosure, i.e., the methods of transmitting process indications are only application to asynchronous HARQ transmissions when rank changes between original transmission and retransmissions.
[0073] While the disclosure has been shown and described in connection with the preferred embodiments, it will be apparent to those skilled in the art that modifications and variations can be made without departing from the spirit and scope of the disclosure as defined by the appended claims. | Asynchronous Hybrid Automatic Repeat reQuest (ARQ) process identities are transmitted in a wireless communication system. A linking scheme is established between at least two sets of process identities of two respective corresponding codewords. When a first process identity is selected from among a first set of process identities of a first codeword, a second process identity may be derived in dependence upon the first process identity and the established linking scheme. Finally, a first packet from the first codeword is transmitted using a first transmission channel indicated by the first process identity, and a second packet is transmitted from the second codeword using a second transmission channel indicated by the second process identity. In addition, a control message including only the first process identity is transmitted. | 7 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates, generally, to the processing of interrupts by a host, and in particular embodiments, to an interrupt notification block that is writeable by a host interface port and readable by the host to reduce the overhead that is involved when the host processes interrupts or has to read information across the host bus.
2. Description of Related Art
A generalized representation of an exemplary conventional computing system is illustrated in FIG. 1 . A computer or server identified generally herein as a host 100 is connected to a host bus 102 (e.g. a PCI-X bus). The host 100 typically includes one or more host processors 114 , cache 116 , and main memory 132 . Also attached to the host bus 102 is at least one port (e.g. a host bus adapter (HBA), an I/O controller, or the like), which is configured by its firmware as an interface to the host 100 and referred to generally herein as a host interface port 104 . The host 100 and the host interface ports 104 may all reside within the same chassis. The host 100 and the host interface port 104 must frequently communicate over the host bus 102 . For example, the host 100 may ask for service from the host interface port 104 via a command, or configure itself to receive asynchronous information, and be notified when the asynchronous information is available or when the commands have been completed. To facilitate these communications, the host 100 includes a command ring 108 and a response ring 110 in main memory 132 , which may comprise a circular queue or other data structure that performs a similar function. In general, rings are used to pass information across the host bus 102 from the host 100 to the host interface port 104 , or vice versa.
The command ring 108 stores command representations such as command I/O control blocks (IOCBS) 148 that are to be presented to the host interface port 104 . A command IOCB 148 contains all of the information needed by the host interface port 104 to carry out a command. When the host 100 writes a command IOCB 148 into the command ring 108 , it also increments a put pointer 144 to indicate that a new command IOCB 148 has been placed into the command ring 108 . When the host interface port 104 reads a command IOCB 148 from the command ring 108 , it increments a get pointer 146 to indicate that a command IOCB 148 has been read from the command ring 108 . In general (excluding for the moment the fact that the command ring 108 is a circular ring that wraps around), if the put pointer 144 is equal to the get pointer 146 , the command ring 108 is empty. If the put pointer 144 is ahead of the get pointer 146 , there are commands 148 in the command ring 108 to be read by the host interface port 104 . If the put pointer 144 is one less than the get pointer 146 , the command ring 108 is full.
The response ring 110 stores response indicators such as response IOCBs 156 of asynchronous events written by the host interface port 104 , including notifications of command completions and of unexpected events. Response IOCBs 156 contain all of the information needed by the host 100 to recognize the completed commands or to handle the unexpected events. For example, one such response IOCB 156 may require that the host 100 initiate a new command. When the host interface port 104 writes a response IOCB 156 into the response ring 110 , it also increments a put pointer 150 to indicate that a new response IOCB 156 has been placed into the response ring 110 . When the host 100 reads a response IOCB 156 from the response ring 110 , it increments a get pointer 152 to indicate that a response IOCB 156 has been read from the response ring 110 .
The host 100 also includes a collection of pointers such as a port pointer array 106 in main memory 132 . The port pointer array 106 contains a list of pointers that can be updated by the host interface port 104 . These pointers are entry indexes into the command ring 108 , response ring 110 , and other rings in the host 100 . For example, the port pointer array 106 contains the get pointer 146 for the command ring 108 and the put pointer 150 for the response ring 110 . When updated, these pointers indicate to the host 100 that a command IOCB 148 has been read from the command ring 108 by the host interface port 104 , or that a response IOCB 156 has been written into the response ring 110 by the host interface port 104 .
The host interface port 104 includes a host bus configuration area 126 . The host bus configuration area 126 contains information that allows the host 100 to identify the type of host interface port 104 and what its characteristics are, and to assign base addresses to the host interface port 104 so that programs can talk to the host interface port 104 .
The host interface port 104 also includes a collection of pointers such as a host pointer array 128 . The host pointer array 128 contains a list of pointers that can be updated by the host 100 . These pointers are entry indexes into the command ring 108 , response ring 110 , and other rings in the host 100 . For example, the host pointer array 128 contains the put pointer 144 for the command ring 108 and the get pointer 152 for the response ring 110 . When updated, these pointers indicate to the host interface port 104 that a command IOCB 148 has been written into the command ring 108 by the host 100 , or that a response IOCB 156 has been read from the response ring 110 by the host 100 . Note that it is relatively inexpensive, from a computational efficiency and overhead standpoint, for the host 100 to initiate writes over the host bus 102 , because once the host 100 puts the data onto the host bus 102 (a “posted write”), no acknowledgement is sent, so the host 100 can proceed with the execution of further instructions without waiting for the write operation to complete.
The host interface port 104 also includes structures such as interface registers 118 , which include a host attention register 120 , a host control register 122 , a host status register 124 , and a mailbox register 154 . The host control register 122 is configurable by the host 100 and contains interrupt enables that identify those attention conditions for which the host 100 would like to receive an interrupt. The host attention register 120 is a concise bitmap of attention conditions of interest to the host 100 . For example, these attention conditions may indicate that there has been an update to the response ring put pointer 150 (which indicates that new responses are available), a link attention condition has occurred, a mailbox operation has completed, or an error condition has occurred.
When the host interface port 104 has completed the processing of a command from the host 100 , the host interface port 104 first examines the get pointer 152 for the response ring 110 stored in the host pointer array 128 and compares it to the known put pointer 150 for the response ring 110 in order to determine if there is space available in the response ring 110 to write a response entry 156 . If there is space available, the host interface port 104 becomes master of the host bus 102 and performs a direct memory access (DMA) operation to write a response IOCB 156 into the response ring 110 , and performs another DMA operation to update the put pointer 150 in the port pointer array 106 , indicating that there is a new response IOCB 156 to be processed in the response ring 110 . The host interface port 104 then writes the appropriate attention conditions into the host attention register 120 , and triggers the generation of an interrupt, if interrupts have been enabled by the host 100 in the host control register 122 .
When an interrupt is received by the host 100 from the host interface port 104 , the host 100 must execute an interrupt handler and a handler for the particular host interface port that initiated the interrupt. The host 100 then initiates a read of the host attention register 120 in the host interface port 104 to determine how to proceed with the interrupt. It is expensive, from a computational efficiency standpoint, for the host 100 to go out over the host bus 102 and read the host attention register 120 in the host interface port 104 , because the host 100 must wait for the operation currently being executed in the host 100 to complete (which may take a long time), other host programs currently being executed must be placed on hold, information from the programs currently being executed must be saved off, the interrupting host interface port must be identified, registers for processing the interrupt must be set up, and the host attention register 120 must be read across the host bus 102 and any other intervening buses to determine the condition being reported so that the host 100 can respond accordingly. While the host attention register 120 is being read, no other processing is occurring in the host 100 . In addition, the host 100 may have to arbitrate with other requesters. In multi-processor systems, a processor may also have to acquire a “lock” which enables that processor to handle the interrupt.
As described above, the contents of the host attention register 120 indicate to the host 100 what has been changed (e.g. a new response has been written into the response ring 110 ), and once notified, the host computer can process the change (e.g. read the response and react accordingly). Once the host 100 has called the appropriate routine to process the interrupt, it can write to the host interface port 104 and clear down those attention conditions in the host attention register 120 that the host 100 is currently handling.
One known method of reducing the number of interrupts that the host 100 must process is called interrupt coalescing. Interrupt coalescing is a request by the host 100 that it not be sent interrupts if it has already performed some processing of responses. If interrupt coalescing is enabled, when the host interface port 104 performs DMA operations to write a response IOCB 156 into the response ring 110 and update the put pointer 150 in the port pointer array 106 , it does not automatically write the appropriate attention conditions into the host attention register 120 . To do so would automatically trigger the generation of an interrupt, if interrupts are enabled in the host control register 122 . Instead, the host 100 is given an opportunity to read the pointers in the port pointer array 106 and read and process the next response IOCB 156 in the response ring 110 when it has an opportunity to do so. After a predetermined amount of time has passed or a predetermined number of response IOCBs 156 have been written into the response ring 110 by the host interface port 104 , the host interface port 104 reads the host pointer array 128 , and if the pointers in the host pointer array 128 indicate that the host 100 is reading response IOCBs 156 from the response ring 110 and making progress in responding to the attention conditions that would ordinarily give rise to an interrupt, then the host interface port 104 may defer writing attention conditions to the host attention register 120 and initiating an interrupt. If, on the other hand, the predetermined amount of time has passed or the predetermined number of response IOCBs 156 have been written by the host interface port 104 into the response ring 110 , but no progress by the host 100 is indicated by the host pointer array 128 , the host 100 needs to be awakened. The host interface port 104 writes the appropriate attention condition information into the host attention register 120 and an interrupt is generated. When the host 100 receives the interrupt, it must incur the expense of reading the host attention register 120 of the host interface port 104 that sent the interrupt.
Despite the improvements in overhead that are possible with interrupt coalescing, there is still a need to further reduce the overhead that is involved when the host processes interrupts or has to read information across the host bus.
SUMMARY OF THE INVENTION
The present invention is directed to an interrupt notification block stored in host memory that provides a copy of attention conditions needed by a host to process responses from a host interface port. This attention condition information has been conventionally stored in a host attention register in the host interface port, and it is very expensive for the host to read these attention conditions from the host attention register across the host bus. By providing these attention conditions in host memory, it reduces the overhead that is involved when the host processes interrupts and reduces the number of times that the host has to read information across the host bus in order to process an interrupt or response.
When the host interface port has completed the processing of a command from the host, the host interface port performs a DMA operation to write a response IOCB into a response ring. The host interface port then performs another DMA operation to update a response ring put pointer in a port pointer array (indicating that there is a new response in the response ring to be processed), and at the same time writes the interrupt notification block, which includes a host attention register (HAR) copy and a counter, by retrieving the appropriate attention conditions from firmware running in the host interface port and writing the HAR copy and counter into host memory.
The HAR copy contains an image of attention conditions that may be stored in the host attention register, including everything the host needs to know to process interrupts, such as the particular rings that need attention. The counter assists the host in determining when the HAR copy has been updated and contains new attention conditions. The value of the counter is changed every time the interrupt notification block is written. When the host reads the HAR copy, it also saves the value of the counter. After the host has acted on the information in the HAR copy, the host can again check the value of the counter. If the value is different, the host knows that new information has been stored in the HAR copy, and must be read from the HAR copy and processed.
After the interrupt notification block is written, if interrupt coalescing is not being utilized, then the host interface port writes the attention conditions into the host attention register, and triggers the generation of an interrupt. Upon receiving the interrupt, instead of reading the host attention register from the host interface port, the host reads the interrupt notification block and processes the interrupt accordingly.
If interrupt coalescing is being utilized, then the host interface port does not automatically write the attention conditions into the host attention register. To do so would automatically trigger the generation of an interrupt. Instead, the host is given an opportunity to read the pointers in the port pointer array and/or the interrupt notification block, which indicates to the host what attention conditions (responses) are pending. The host may process some of the responses it has received when it has an opportunity to do so, and update the pointers in the host pointer array to indicate to the host interface port that the host is making progress in processing the responses.
If, on the other hand, no progress by the host is indicated over a predetermined amount of time, or if a predetermined number of response entries has been stored by the host interface port into the response ring without progress by the host, the host needs to be awakened. The host interface port will then update the attention conditions in the host attention register and generate an interrupt. However, instead of performing the expensive read of the host attention register, the host can simply read the interrupt notification block to process the response. When the host has fully processed the response from the host interface port, the host performs a write to the host attention register to clear the appropriate interrupt conditions.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 illustrates a conventional computing system and the registers, arrays and rings required for interrupt processing.
FIG. 2 illustrates a computing system utilizing an interrupt notification block according to embodiments of the present invention.
DETAILED DESCRIPTION OF PREFERRED EMBODIMENTS
In the following description of preferred embodiments, reference is made to the accompanying drawings that form a part hereof, and in which is shown by way of illustration specific embodiments in which the invention may be practiced. It is to be understood that other embodiments may be utilized and structural changes may be made without departing from the scope of the preferred embodiments of the present invention.
FIG. 2 illustrates a computing system according to a specific, preferred embodiment of the present invention that is similar to that conventional system of FIG. 1 , except that an interrupt notification block 238 is part of the port pointer array 206 . The interrupt notification block 238 includes a host attention register (HAR) copy 240 and a counter 242 . However, it should be understood that the HAR copy 240 and counter 242 could be replaced with other data structures or circuits that perform the same function as understood by those skilled in the art.
When the host interface port 204 has completed the processing of a command from the host 200 , the host interface port 204 first examines the get pointer 252 for the response ring 210 stored in the host pointer array 228 and compares it to the known put pointer 250 for the response ring 210 in order to determine if there is space available in the response ring 210 to write a response IOCB 256 . If there is space available, the host interface port 204 becomes master of the host bus 202 and performs a DMA operation to write a response IOCB 256 into the response ring 210 . The host interface port 204 then performs another DMA operation to update the put pointer 250 in the port pointer array 206 (indicating that there is a new response in the response ring 210 to be processed), and at the same time writes the interrupt notification block 238 (HAR copy 240 and counter 242 ) by retrieving the appropriate attention conditions from the firmware running in the host interface port 204 and writing the HAR copy 240 and counter 242 into host memory.
The HAR copy 240 contains an image of the attention conditions that may be stored in the host attention register 220 , including everything the host 200 needs to know to process interrupts, such as the particular rings that need attention. Note that the HAR copy 240 contains not only information related to new attention conditions that the host 200 needs to be aware of, but also information related to other attention conditions that have not been handled yet. In other words, it is an accumulation of all of the information related to all of the attention conditions that the host 200 needs to handle. The host 200 can thereafter access the information in the HAR copy 240 without needing to read the host attention register 204 in the host interface port 204 .
Note that the host 200 need not receive an interrupt from a host interface port 204 in order to process attention conditions in the HAR copy 240 . The host 200 can, at any time when it is available and able to do so, read the HAR copy 240 and process attention conditions. To assist the host 200 in determining when the HAR copy 240 has been updated and contains new attention conditions, the interrupt notification block 238 also includes a counter 242 , which is also written by the host interface port 204 to change the value of the counter 242 every time the interrupt notification block 238 is written. When the host 200 reads the HAR copy 240 , it also saves the value of the counter 242 . After the host 200 has acted on the information in the HAR copy 240 , but before getting out of the interrupt handling level, the host 200 can again check the value of the counter 242 . If the value is different, the host 200 knows that new information has been stored in the HAR copy 240 , and must be read from the HAR copy 240 and processed.
After the interrupt notification block 238 is written, if interrupt coalescing is not being utilized, then the host interface port 204 writes the HAR copy information into the host attention register 220 , and triggers the generation of an interrupt, if interrupts are enabled in the host control register 222 . Upon receiving the interrupt, instead of reading the host attention register 220 from the host interface port 204 , the host 200 reads the interrupt notification block 238 and processes the interrupt accordingly.
If interrupt coalescing is being utilized, then the host interface port 204 does not automatically write the HAR copy information into the host attention register 220 . To do so would automatically trigger the generation of an interrupt, if interrupts are enabled in the host control register 222 . Instead, the host 200 is given an opportunity to read the pointers in the port pointer array 206 and/or the interrupt notification block 238 , which indicates to the host 200 what attention conditions (responses) are pending. The host 200 may process some of the responses it has received when it has an opportunity to do so, and update the pointers in the host pointer array 228 to indicate to the host interface port 204 that the host 200 is making progress in processing the responses. For example, the host interface port 204 can read the get pointer 252 in the host pointer array 228 , and if the get pointer 252 indicates that the host computer is reading the responses in the response ring 210 and making progress in responding to the attention conditions that would ordinarily give rise to an interrupt, then the host interface port 204 may not write to the host attention register 220 and initiate an interrupt.
If, on the other hand, no progress by the host 200 is indicated over a predetermined amount of time, or if a predetermined number of response entries has been stored by the host interface port 204 into the response ring 210 , the host 200 needs to be awakened. The host interface port 204 will then update the attention conditions in the host attention register 220 and generate an interrupt. However, instead of performing the expensive read of the host attention register 220 , the host 200 can simply read the interrupt notification block 238 to process the response.
When the host 200 has fully processed the response from the host interface port 204 , the host 200 performs a write to the host attention register 220 to clear the appropriate interrupt conditions.
A software driver executable on the host 200 , and firmware executable on the host interface port 204 may be written to implement the embodiments of the present invention described above. However, in alternative embodiments, the features described above may be implemented in software, firmware, or hardware.
If a software driver incorporating the embodiments of the present invention described above is initialized, it will poll the host interface port 204 to determine if the host interface port 204 supports an interrupt notification block 238 . If the host interface port 204 includes firmware that incorporates the embodiments of the present invention described above, an affirmative response will be received by the software driver, and more efficient communications between the host 200 and the host interface port 204 will occur utilizing the interrupt notification block 238 as described above. If the host interface port 204 does not include firmware that incorporates the embodiments of the present invention described above, an affirmative response will not be received. In such a case, the interrupt notification block 238 will not be written and, without the benefit of the interrupt notification block 238 , communications between the host 200 and the host interface port 204 will occur as described in the Background section above.
If a software driver that does not incorporate the embodiments of the present invention described above is initialized and configured, it will not configure itself to recognize an interrupt notification block 238 . If the host interface port 204 also does not include firmware that incorporates the embodiments of the present invention described above, then of course communications between the host 200 and the host interface port 204 will occur as described in the Background section above. Even if the host interface port 204 includes firmware that incorporates the embodiments of the present invention described above, and attempts to write the interrupt notification block 238 , it will not be successful. Without the benefit of the interrupt notification block 238 , communications between the host 200 and the host interface port 204 will occur as described in the Background section above.
Although the present invention has been fully described in connection with embodiments thereof with reference to the accompanying drawings, it is to be noted that various changes and modifications will become apparent to those skilled in the art. Such changes and modifications are to be understood as being included within the scope of the present invention as defined by the appended claims. | An interrupt notification block stored in host memory is disclosed that contains an image of the interrupt condition contents that may be stored in a host attention register in a host interface port. The interrupt notification block is written by the host interface port and pre-fixed into the port pointer array of a host at the time the host interface port updates the pointers stored in a port pointer array in host memory. The host may then read the interrupt notification block to determine how to process a response or an interrupt rather than having to read the host attention register in the host interface port across the host bus. | 6 |
BACKGROUND OF THE INVENTION
1. Technical Field
This device relates to tonneau covers for truck beds that utilize a support and fastening frame on the bed for selectively securing a cover over the opening defined thereby.
2. Description of Prior Art
Prior art devices of this type have used a variety of different cover and frame configurations to support and secure the cover over the open truck bed against inclement weather and foreign debris. Such covers also conceal cargo and improve the aerodynamics by imparting a flush, smooth, wind resistant surface to the truck bed. A number of fastening methods have been developed including the traditional snap fasteners in which the perimeter edge of the cover is registerably secured to a support rail frame by pairs of interconnecting mechanical snaps. Fabric securing systems utilizing hook and loop fastening elements have also been used; see for example U.S. Pat. Nos. 4,272,119 and 4,757,854.
Quick removable cover assemblies can be seen in U.S. Pat. Nos. 3,804,766, 4,762,360 and 4,792,178.
A number of hinge cover assemblies have been developed in prior art that allow easy access to the truck bed by lifting up a portion or all of the cover on a separate self-supporting frame held open by lift arms, see U.S. Patents Applicants own U.S. Pat. Nos. 5,301,995 and 5,511,843 are directed towards tonneau cover assemblies with transverse support bows extending between respective side parallel mounting rails.
SUMMARY OF THE INVENTION
A tonneau cover for truck beds that provides a detachable retractable cover selectively attached to a support frame which is secured along portions of the perimeter edge of the truck bed defining an opening. The cover has an elongated contoured end rail that is resiliently engaged between spaced parallel fixed support rails utilizing spring urged stretching brackets with a locking and release retention latch configuration.
DESCRIPTION OF THE DRAWINGS
FIG. 1 is a perspective view of a truck bed with the invention installed in partial retractable position thereon;
FIG. 2 is an enlarged partial perspective view of an inner engagement retaining element for the bed cover of the invention;
FIG. 3 is a partial side elevational view of the retaining element in fully engaged position in solid lines and disengaged in multiple broken lines;
FIG. 4 is an enlarged partial top plan view of the retaining assembly as seen in FIG. 3 of the drawings;
FIG. 5 is an enlarged partial bottom plan view of the retaining assembly as seen generally in FIGS. 3 and 4 of the drawings;
FIG. 6 is a bottom plan view of the cover assembly of the invention with portions broken away;
FIG. 7 is an enlarged side elevational view of a portion of the release assembly for the retaining assembly seen in FIGS. 5 and 6 of the drawings;
FIG. 8 is an enlarged partial cross-sectional view of a front support mounting and rail of the invention;
FIG. 9 is an enlarged partial top plan view of the front support and mounting rail of the invention;
FIG. 10 is an enlarged partial cross-sectional view of the support rail secured to the respective side of the truck bed;
FIG. 11 is a partial side elevational view of the tonneau cover of the invention in partial retractable position; and
FIG. 12 is a partial end elevational view of the retaining rail assembly of the invention with portions broken away.
DESCRIPTION OF THE PREFERRED EMBODIMENT
Referring to FIG. 1 of the drawings, a retractable tonneau cover assembly 10 can be seen installed on a truck 11 having a cab portion 12 , a bed portion 13 and wheel assemblies 14 . The bed portion 13 has oppositely disposed parallel sidewalls 15 and 16 and an interconnecting end wall 17 adjacent the cab portion 12 . A hinge tailgate 18 is movably disposed between the open ends of the sidewalls 15 and 16 thus defining the interior of the truck bed.
The retractable tonneau cover assembly 10 of the invention has a main support frame 19 comprised of oppositely disposed elongated support side rails 20 and 21 which are interconnected by a front rail 22 secured thereto forming a generally U-shaped configuration as best seen in FIGS. 1 and 6 of the drawings.
Each of the respective side rails 20 and 21 are formed from an identical metal extrusion having a wall engagement portion 22 A and a tonneau engagement portion 22 B. The wall engagement portion 22 A has a vertically oriented engagement surface 24 extending there from with an offset transition area 25 . The tonneau engagement portion 23 has a base element 26 with an upstanding curved element 27 extending there from, best seen in FIGS. 2 and 10 of the drawings. The side rails 20 and 21 are secured to their respective side walls 15 and 16 of the truck bed portion 13 by a plurality of longitudinally spaced mechanical clamps 28 . Each of the clamps 28 is formed of a two-part construction with a sidewall engagement bracket 28 A and an interdisposed rail engagement bracket 28 B in slidably disposed relation. The brackets 28 A and 28 B are adjustably secured to one another by a threaded fastener 28 C as seen in FIG. 10 of the drawings which is common within the industry.
Referring now to FIGS. 6, 8 and 9 of the drawings, the front rail 22 of the invention can be seen secured between the respective ends of the side rails 20 and 21 adjacent the cab portion 12 of the truck 11 as noted. The front rail 22 is secured by a pair of fasteners F extending from a channel 22 A through inner aligned apertures A in the respective side rails base 26 as will be well understood by those skilled in the art and as best seen in FIG. 8 of the drawings. The front interconnecting rail 22 is preferably of a metal extrusion configuration having a contoured upper surface 23 with an elongated cover engagement and attachment surface 23 A and oppositely disposed end portion 23 B. The cover engagement and attachment surface 23 A having an elongated arcuate channel 23 C formed therein.
A fabric cover 29 of the tonneau cover assembly 10 is secured along its front edge 29 A to a synthetic resin channel insert 28 which is in turn slidably disposed within a respective channel 23 C therein effectively securing the front edge of the cover through the front interconnecting rail 22 . Resilient engagement assemblies 30 can be seen having a sliding block 31 with a tapered engagement end wall 32 . A guide fastener 33 extends from the block 31 through an elongated guide opening 34 in the base 26 of the respective side rails 20 and 21 . A spring assembly 38 extends from an L-shaped mounting bracket 36 secured to the base 26 of the respective rails in spaced relation to the blocks 31 .
The spring assemblies 38 have a spring retainer 38 A with a spring 38 B extending there from for engaging the sliding block 31 providing a resilient retention thereto as indicated by directional arrows. The engagement assemblies 30 are positioned inwardly of the respective free ends 20 A and 21 A of the side rails 20 and 21 and provide a positive resilient engagement for the cover 29 as will be hereinafter described.
Referring now to FIGS. 2 and 3 of the drawings, a retractable engagement end rail 40 extrusion can be seen identical to that of front rail 22 having a contoured upper surface 41 with an elongated engagement surface 42 and an oppositely disposed cover attachment end portion 43 . The engagement surface 42 is a an elongated half circular surface that is pivotally engaged during use under the tapered end walls 32 of the respective blocks 31 as seen in broken lines in FIG. 3 of the drawings.
The cover attachment end portion 43 has a contoured surface 44 with a circular elongated mounting channel 45 therein. An elongated cover engagement fitting 46 is attached along a back edge 47 of the cover 29 by conventional means and is slidably positioned within the respective mounting channel 45 thus securing the free edge of the cover 29 to the front rail 22 .
It will be seen that the engagement portion 42 of the end rail 40 is initially engaged against the tapered end walls 32 of the respective blocks 31 as seen in broken lines in FIG. 3 of the drawings. The engagement portion 42 is then, as noted previously, pivoted downwardly as seen in broken lines against the tension of the fabric cover 29 displacing the sliding blocks 31 against their respective springs 38 B until full engagement with respective side rails 20 and 21 as illustrated in solid lines in FIG. 3 of the drawings is achieved.
The fabric cover 29 as seen in FIGS. 1, 6 and 8 of the drawings extends when deployed over the frame 19 in a stretched taunt fashion. In order for the cover 29 to be supported over the truck bed, it has a plurality of longitudinally spaced transverse support ribs 48 attached to an under surface 29 A of the cover by engagement of a plurality of fabric elastic pockets 49 extend in spaced longitudinal relation to one another along the oppositely disposed perimeter edges 50 of the cover 29 . The ribs 48 are inserted therein by their ends, as best seen in FIGS. 6 and 8 of the drawings. The cover 29 is removably secured to the respective rails 20 and 21 by strips of hook and loop material M on their respective outer curved surfaces 27 and correspondingly aligned strips of hook and loop material M secured along the cover's underside respective longitudinal side edges 51 and 52 as seen in FIGS. 9 and 10 of the drawings.
A locking assembly 53 is mounted to the underside of the end rail 40 , best seen in FIGS. 5, 6 , 7 and 12 of the drawings having a pair of oppositely disposed spring urged locking slides 54 and 55 which are mounted within a channel 56 formed in the under surface of the end rail 40 . Each of slides 54 and 55 having a contoured body member 57 with a tapered engagement end surface 58 and an upstanding spring retainer and guide 59 assembly which slidably retains the respective slides 54 and 55 within the channel 56 between pairs of limit fittings 60 A and 60 B.
Referring now specifically to FIGS. 7 and 8 of the drawings, the limit fittings 60 A and 60 B are illustrated as defining a travel path for the respective slides 54 and 55 indicated by directional arrows TP. The respective safety slides 54 and 55 will registerably extend over the respective edges 61 of the side rail base 26 by the spring retainer and guide assembly 59 . Each of the safety slides 54 and 55 have a release strap 62 and 62 A respectively extend there from to strap fastener 62 C and 62 D secured to the channel 56 by fasteners F. They can be used selectively to retract the slides 54 and 55 allowing the end rail 40 to be released from engagement with the engagement assemblies 30 .
Once the end rail 40 is released it is used as a core to roll up the cover 29 thereon as illustrated in FIGS. 1 and 11 of the drawings. As the cover 29 is rolled up, it will release from the respective side rails 20 and 21 allowing access to the truck bed 13 .
It will be evident from the above description that once fully rolled up, the cover 29 is secured by a pair of retaining straps 63 and 64 having hook and loop material on their respective end surfaces 63 A and 64 A safety storing the cover 29 in rolled up fashion over the front rail 22 of the tonneau cover assembly 10 .
To deploy the cover 29 the respective strap pairs 63 and 64 are released and the cover 29 unrolled until the end rail 40 is exposed and then resiliently engaged against the respective sliding blocks 31 which yield as the end rail 40 is pivoted into place against the respective rails 20 and 21 and secured thereto by the automatic registration of the hereinbefore described safety slides 54 and 55 . The inner engagement i.e. interlocking of the respective hook and loop material M along the side rails 20 and 21 and the aligned, now engaged longitudinal edges of the cover 29 are confirmed, securing the cover 29 tautly in place over the truck bed 13 .
As noted, it is an important aspect of the hereinbefore described cover assembly 10 of the invention is that the cover 29 when deployed is temporarily held in place on the support frame by engagement of the end rail 40 under the tension of the cover 29 with the resilient locking blocks 31 of the respective engagement assemblies 30 . The respective slides 54 and 55 lock the cover in place.
It will thus be seen that a new and novel tonneau cover configuration for a pick-up truck bed has been illustrated and described and it will be apparent to those skilled in the art that various changes may be made therein without departing from the spirit of the invention. | A tonneau cover assembly for use on sports trucks to cover the truck bed. The tonneau cover assembly allows for removable access to the truck bed without fully removing the cover from the truck. A multiple rail support and mounting frame is secured around the perimeter of the truck bed opening with a fabric cover releaseably secured along an upper portion of the frame's upstanding and fixed edges. An end rail secured to the cover is resiliently positioned between oppositely disposed spring urged assemblies on respective rails to stretch the cover in place and then to be secured by independent locking elements resiliently extending from the end rail. | 1 |
FIELD OF THE INVENTION
This invention relates to a safety check unit for use in a liquid distribution system, having a pump for distribution of the liquid, to protect equipment of the system from damage associated with loss of pumping capability.
BACKGROUND OF THE INVENTION
In a liquid distribution system, such as a municipal water or sewage system, a pump is typically provided at least at one end of the distribution system so as to provide the pressure required for distributing the liquid throughout the system. An example of a system of concern is a municipal water system wherein water from a reservoir, for example, is pumped through a series of water mains for eventual distribution to homes, commercial establishments, industrial facilities, and the like. In such a system, it is prudent to protect the pump and associated equipment from damage which could occur if the pump, for whatever reason, suddenly loses head pressure and stops pumping. When such an event occurs, damage can be caused to the pump, distribution manifolds, piping and other equipment associated with the pump.
A number of conditions caused by the sudden loss of pumping pressure must be addressed within seconds of the pressure loss in order to prevent damage to the mentioned equipment. The conditions include: 1) the presence of a negative pressure (in relation to atmospheric pressure) within manifolds, pipelines, fittings, valve bodies, etc. near the pump which potentially can cause cracking or structural failure of those components; 2) a back-flowing of the liquid in the system, with an impact which potentially can cause severe structural damage to the pump, manifolds, pipeline, fittings, valve bodies etc. in the vicinity of the pump; and 3) if such conditions are not addressed properly, pockets of air which can form and which can cause problems upon start-up of the system following the loss of pumping pressure.
Prior art means to overcome the conditions which threaten the pump and related equipment have been cumbersome and complex, they involve many man hours for installation and they require a large amount of space in pumping station facilities. Use of a number of components, each to address a different condition described above, and installed in different locations, increases the possibility of component failure and leakage at joints connecting the piping and the components. Mismatching of size or capacity of the components does not provide the optimum protection. Extensive engineering analysis to match all of the components to each other and to the overall system is required. High labor cost and often compromised assembly of the components, under field conditions, can result in future occurrences of leaks and the like. Positioning of the various components at locations in the system, which may not be the critical location for operating in an optimum manner when loss of pressure or surge occurs, compromises the system.
The various devices, which previously have been provided for controlling the above-mentioned threats to the system include: 1) a check valve, which ideally is piped into the system immediately down stream of the system pump; 2) a surge relief valve, usually positioned at an end of a manifold of the system, but remote from the pump, for receiving and relieving the above-described back-flow surge resulting from the loss of pumping pressure, and 3) an air/vacuum valve, also usually provided at an end of a manifold, or other various locations in the system at a location remote from the pump, to allow air into the system when negative pressure within the system is detected, so as to prevent a vacuum condition, and to allow that air out of the system prior to or during normal operating conditions.
In the present disclosure of the apparatus of the invention, terms such as upstream, downstream, and the like, are used in relation to the flow of the liquid being pumped in a direction to supply the liquid under pressure from the liquid source, through the liquid distribution system to the residential, commercial, and industrial users.
OBJECTS OF THE INVENTION
It is an object of the present invention to provide a compact device which incorporates all of the functions necessary to protect a pump, and associated components of a liquid distribution system, from structural damage caused by a sudden drop in the pumping pressure of the pump.
It is another object of the present invention to dispose components of the device, and sensing means required for operation of each component, at an optimum location in the distribution system, and to have components configured for optimum effectiveness in overcoming detrimental conditions.
It is yet another object of the invention to provide a device having all of the features properly sized in relation to each other and integrated for optimum performance, and to provide a device which can be incorporated into a liquid distribution system at solely one critical point of insertion into the system.
It is still another object of the invention to provide a device requiring no electrical, hydraulic or other external support, and requiring no intervention of operating personnel for damage controlling operation of the device or for returning the device back to normal operating conditions following return of the pumping pressure.
SUMMARY OF THE INVENTION
The present invention is a safety check unit for use in a liquid distribution system which has a pump and a piping network downstream of the pump for distributing the pumped liquid, wherein the pump intakes a liquid at an intake pressure and outputs the liquid to the piping network at an output pressure which is greater than the intake pressure; and upon terminating pumping, the liquid in the pipe network exerts a back-pressure at the pump which is greater than the intake pressure. The unit is configured for placement in communication with the liquid distribution system downstream of the pump and includes: a liquid checking portion, for checking liquid when back-flowing from the piping network toward the pump, the liquid checking portion having an inlet port in communication with the pump, an outlet port in communication with the distribution system, an internal chamber intermediate the ports and a closing member disposed in the internal chamber for preventing back-flowing of the liquid; a surge relief portion, communicating directly with the internal chamber, for relieving liquid from the system and reducing liquid pressure in the system rapidly when the liquid pressure in the internal chamber is above a pre-selected pressure which is greater than an operating output pressure of the pump; an air input portion, communicating directly with the internal chamber, for providing air to the system when the internal chamber is at least partially void of liquid and a pressure in the void is below atmospheric pressure; and an air release portion, communicating directly with the internal chamber, for releasing air from the system at an adjustable speed when air is in the internal chamber at a pressure above atmospheric pressure.
DESCRIPTION OF THE DRAWINGS
The invention will become more readily apparent from the following description of the embodiments thereof which are shown, by way of example only, in the accompanying drawings, wherein;
FIG. 1 is a schematic diagram of a fluid distribution system which incorporates the device of the present invention;
FIG. 2 is a vertical cross-section of the device of the present invention showing components positioned as they would be during normal pumping conditions;
FIG. 3 is a vertical cross-section of the device of the present invention showing components positioned as they would be just following a sudden loss of pumping pressure and liquid flowing due to momentum of the liquid;
FIG. 4 is a vertical cross-section of the device of the present invention showing components positioned as they would be when liquid flow due to momentum has stopped;
FIG. 5 is a vertical cross-section of the device of the present invention showing components positioned as they would be just following an initial stage of a surging back-flow of liquid;
FIG. 6 is a vertical cross-section of the device of the present invention showing components positioned as they would be near the end of a surging back flow of liquid;
FIG. 7 is a vertical cross-section of the device of the present invention having an alternative surge pressure relief means.
FIG. 8 is a vertical cross-section of the device of the present invention having an alternative liquid checking portion, surge pressure relief portion, and air input/release portion;
FIG. 9 is a vertical cross-section of the device of the present invention having an alternative liquid checking portion, surge pressure relief portion, air input portion, and air release portion;
FIG. 10 is a vertical cross-section of the device of the present invention having an alternative liquid checking portion and air input/release portion;
FIG. 11 is a partial vertical cross-section of the device of the present invention having an alternative liquid checking portion; and
FIG. 12 is a vertical cross-section of the device of the present invention having an alternative liquid checking portion, surge pressure relief portion, and air input/release portion.
DETAILED DESCRIPTION
The present invention can be incorporated into any system wherein a liquid is being pumped under pressure to a distribution network, or the like, and wherein, if the pumping pressure suddenly drops, the already pumped liquid would return toward the pump under pressure as a surging back-flow.
Liquid systems, which should incorporate the present device, for protection of components of the system, include municipal water systems, municipal sewage systems, oil or other liquid pipeline systems, and industrial processing systems. For purposes of disclosing the present invention, one type of a municipal water system will be described. FIG. 1 shows a municipal water system having a water source 1 . Water is pumped by a water pump 2 through piping 3 to a water storage tank 4 for distribution to homes, commercial establishments, industrial facilities, and the like through distribution pipes of a municipal water distribution system 5 . In such a distribution system, the pump 2 must provide an output pressure in excess of a back pressure resulting from gravity acting on the water of the system. The amount of back pressure is dependent on the height h from the pump to the top surface of the water in storage tank 4 . It is that back pressure, which if unchecked, can cause severe damage to the pump and associated equipment of the pumping facility if a sudden drop in pumping pressure occurs. Such a sudden drop in pumping pressure can occur, for example, if electrical power to the pump is interrupted. The device of the invention, a safety check unit 6 , is preferably installed in the water distribution system immediately downstream of the pump 2 as depicted in the schematic diagram of FIG. 1 .
FIG. 2 shows a vertical cross-section of the safety check unit 6 of the invention. The unit is installed so as to be in direct communication with the water being pumped and is preferably installed adjacent to the pump or a short distance from the pump in a header, manifold, or piping of the system, with use of flanges 7 . A body 8 of the unit defines an internal chamber 9 through which the pumped water travels in a direction indicated by arrow 10 as it flows from inlet port 11 to outlet port 12 . The body 8 has formed therein an annular seat 13 upon which closing member 14 pivotally closes to prevent back flowing of the water when the pumping pressure is less than the back pressure of the distribution system. FIG. 2 depicts the closing member 14 in an “open” position and FIGS. 3-7 depict the closing member 14 in a “closed” or “checking” position. In the preferred embodiment of the invention the manner of operation of the closing member is by a pivotal or swinging type movement about axis 15 . Various other mechanisms for providing the checking action are possible. Other mechanisms providing checking action are piston action, poppet action, tilting disc action, spring loaded action, etc.
The device of the invention includes other portions, which are also in direct communication with chamber 9 . Such direct communication with that chamber provides for optimum operation of the device and greatest protection for the equipment of the pumping system. The other portions of the device include a surge relief portion 16 which communicates with chamber 9 through, relief inlet port 17 , and a combination air-vacuum portion 18 which communicates with chamber 9 through piping 19 . In other embodiments of the invention the air-vacuum portion is made up of a separate air input portion and a separate air release portion.
A sequence of events, which most likely occurs when pumping pressure is suddenly lost, is described with reference to FIGS. 2-6. The functions carried out by safety check unit 6 , in response to those events, are also described.
FIG. 2 shows safety check unit 6 in normal operation, that is, the pump is providing a liquid pressure at the outlet port 12 which is greater then the back pressure of the liquid distribution system. Therefore, liquid 20 is flowing in the direction indicated by arrow 10 from inlet port 11 to outlet port 12 . The force of the flowing liquid overcomes the gravitational force on closing member 14 and closing member 14 is in the open position. In normal operation, surge relief portion 16 is blocking the escape of liquid by way of differential piston 21 blocking channel 22 which communicates with relief port 17 . A pilot valve 23 , which is used to control the surge relief portion 16 has opening 24 closed by the pressure of spring 25 . Air/vacuum portion 18 has opening 26 closed by float assembly 27 which floats in chamber 28 in the liquid of the distribution system which fills that chamber. With safety check unit 6 having its components positioned as described, all of the pumped liquid entering inlet port 11 exits outlet port 12 for delivery to the liquid distribution system as no other outlet path is open.
If a pump failure occurs, the following series of events most likely would take place in the distribution system. First in the sequence of events, the supply of liquid to inlet port 11 by the pump is terminated and the entrance of liquid or air past pump 2 and into the system through inlet port 11 is in most cases blocked by the mechanism of the pump. Without the flow of liquid, closing member 14 first drops by gravity to a position on annular seat 13 as depicted in FIG. 3 .
Next, in the sequence of events, due to the momentum of the flowing (already pumped) liquid, a liquid column separation may occur whereby chamber 9 becomes at least partially empty of liquid and a near vacuum condition tends to occur in chamber 9 . The near vacuum condition can extend partially into the pipe or manifold downstream of outlet 12 as shown in FIG. 3 . Such a vacuum condition, which could have a damaging affect on the system, is averted by action of the air-vacuum portion 18 of the safety check unit. Opening 26 is opened by movement of float 27 downward in the now liquid-depleted chamber 28 by the force of gravity, so as to allow air into chamber 9 by way of piping 19 . Air-vacuum portion 18 allows air into the chamber 9 when no liquid is present in chamber 28 containing float 27 and pressure in a void of chamber 9 is less than atmospheric pressure.
Next, in the sequence of events, as the momentum of the flowing liquid diminishes, the flow of liquid stops as depicted in FIG. 4 . Closing member 14 remains against annular seat 13 , air vacuum portion 18 remains open due to float 27 being displaced from opening 26 , and surge relief portion 16 remains closed.
Next, in the sequence of events, the flow of liquid reverses and surges toward pump 2 as depicted in FIG. 5 . Air in the system, which entered the system in order to prevent a vacuum condition, is now released from the system by way of the air/vacuum portion 18 . Also, entrapped air from the liquid is released. Referring to FIG. 5, air-vacuum portion 18 has opening 26 in the open position since air is still present in chamber 28 and the float 27 is not floating. Air is released by the air/vacuum portion when the air is at a pressure greater than atmospheric pressure, as is the case when the liquid is back-flowing. The rate at which the air leaves the system can be restricted or regulated by throttling device 36 which is in communication with opening 26 of air/vacuum portion 18 . In addition to the float action air/vacuum valve described above, spring type, and diaphragm type mechanisms can be incorporated. Additionally, a weight loaded type air input mechanism can be incorporated. By releasing the air at a selected rate, the air helps to cushion the surging back-flow of liquid.
As described above, closing member 14 is closed against seat 13 initially by the force of gravity alone and then by the force of the back-flowing liquid. Following removal of air in the system, liquid enters chamber 28 and float 27 floats to close off opening 26 . The pressure in chamber 9 increases, due to the surging back-flow of liquid. To relieve the pressure of the surging back-flowing liquid, differential piston 21 of surge pressure relief portion 16 displaces upwardly as shown in FIG. 6 to allow the surging liquid pressure to be relieved through outlet port 29 . The pressure at which differential piston 21 displaces upwardly is pre-selected and is set at a value which is greater than the normal operating pressure of the pump. The differential piston 21 remains upwardly displaced until the pressure in chamber 9 is less than that set pressure. The pre-selected pressure is set by means of relief pilot valve 23 . Relief pilot valve 23 senses the pressure in chamber 9 through sensing tube 30 . During normal pumping operation of the distribution system (FIG. 2 ), differential piston 21 of the surge pressure relief portion 16 has liquid of equal pressure on faces A and B as face A communicates with chamber 9 by way of channel 22 and face B communicates with chamber 9 by way of piping 31 and 32 . However, since face A has a smaller surface area than face B, the net force on the piston is downward, thus closing off channel 22 . If the pressure in chamber 9 , which is conveyed to relief pilot valve 23 through sensing tube 30 increases, due to the surging back-flow, to a pressure above the pre-selected pressure set for relief pilot valve 23 , spring 25 is overcome by that pressure and valve opening 24 of the relief pilot valve 23 opens to the atmosphere so as to drop the pressure in piping 33 and 32 as well as the pressure against face B of differential piston 21 . The pressure against face B is then such that the net force on differential piston 21 is in the upward direction thus allowing the surging pressure to be relieved by way of channel 22 and outlet port 29 .
After the surging pressure is relieved and the pressure within chamber 9 becomes less than the pre-selected pressure, relief pilot valve 23 closes by action of spring 25 , liquid pressure on faces A and B of differential piston 21 becomes substantially equal again, and, due to the difference in surface areas of the faces, the piston is forced to the downward closed position again. The speed at which the piston moves to the closed position can be controlled with use of closing speed control valve 34 which meters the liquid flowing toward face B of the differential piston. Speed control valve 34 is preferably a needle valve, but can be any of various other means of regulating flow so as to better control the flow of liquid so as to prevent a secondary surge of liquid which would result from differential piston 21 closing too quickly. In order to prevent clogging of needle valve 34 , a strainer 35 is preferably disposed in piping 31 ahead of speed control valve 34 .
Following the closing of outlet port 29 by differential piston 21 , components of the safety check unit are disposed for normal pumping operation. When pumping is resumed, components of the safety check unit are disposed as depicted in FIG. 2, without intervention of operating personnel.
An important feature of the safety check unit of the invention is the common chamber with which all of the portions of the unit directly communicate. With such direct communication, each of the actions required by the different portions of the unit to protect the pump, and other components of the distribution system, takes place in a very short period of time so as to provide maximum protection to the pump and associated equipment.
A second embodiment of the invention provides surge pressure relief in a different manner. Referring to FIG. 7, surge pressure relief portion 37 relieves surging back-pressure of the liquid, as described above, by movement of valve 38 in an upward direction so as to open chamber 22 . During normal operation of the system, valve 38 is held in a closed position by spring means 39 . The pressure required for opening valve 38 is preselected and set by adjustment of the spring mechanism. In addition to the surge pressure relief valves described above, diaphragm operated, lever and weight, spring loaded and other type actions can be incorporated into the unit.
FIGS. 8-12 show the safety check unit of the invention having portions using various other mechanisms to carry out the functions of the device.
In FIG. 8, safety check unit 40 incorporates a spring loaded action liquid checking portion 41 , a spring loaded action surge relief portion 42 and a float action air input/air release portion 43 .
In FIG. 9, safety check unit 44 incorporates a poppet action liquid checking portion 45 , a spring loaded action surge relief portion 46 , a weight loaded valve action air input portion 47 , and a float action air release portion 48 .
In FIG. 10, safety check unit 49 incorporates a tilting disk action liquid checking portion 50 , a piston action surge relief portion 51 , and a diaphragm action air input/air release portion 52 .
In FIG. 11, safety check unit 53 incorporates a spring loaded action liquid checking portion 54 , a piston action surge relief portion 55 and a float action air input/air release portion 56 .
In FIG. 12, safety check unit 57 incorporates a piston action liquid checking portion 58 , a spring loaded action surge relief portion 59 , and a float action air input/air release portion 60 .
In all of the above described safety check units the liquid checking portions of each includes an internal chamber 9 which communicates directly with the surge relief portion, the air input portion, and the air release portion.
While specific configurations of the components have been set forth for purposes of describing embodiments of the invention, various modifications can be resorted to, in light of the above teachings, without departing from applicant,s novel contributions; therefore in determining the scope of the present invention, references shall be made to the appended claims. | A safety check unit for use in a liquid distribution system for preventing damage to a pump and associated components of the system in event of loss in pumping pressure. The unit provides a check component to prevent back-flow of the liquid when the pump is shut down, and provides protection against a possible vacuum condition in the system by introducing air to the system; protects against damage by a surging back-flow of liquid by opening a relief port of the unit; and protects against air in the system by use of an air relief mechanism of the unit. | 8 |
TECHNICAL FIELD
[0001] The present invention relates to an implant playing a role as a joint in coupling a revision implant in revision total knee arthroplasty and, more specifically, to an offset adapter unit comprising an adapter which couples a femoral member or a tibial member to a stem member in revision total knee arthroplasty; and a nut coupled to the adapter, thereby improving the strength by taking into consideration fracture occurring in the narrowest area.
BACKGROUND
[0002] There are joints, being parts connecting bones and capable of freely moving, in a human body. Of the joints, the largest joint is the knee joint. The knee joint is disposed in a middle part of a leg and consists of a tibiofemoral joint and a patellofemoral joint.
[0003] The knee joint replacement surgery is performed when there is trouble walking or discomfort in daily activities due to severe pain in the knee joint and degenerative arthritis. However, even after surgery there can be a case where pain occurs again and walking becomes problematic as time passes. Then reoperation may be done after diagnosis, which is called revision total knee arthroplasty.
[0004] However, it is difficult to firmly fix an artificial joint in the revision total knee arthroplasty, unlike in the knee joint replacement surgery, because of lack of strong bones as bones around the artificial joint had already been melted at the time of the revision total knee arthroplasty. Thus, fixing force of a replacement should be reinforced by attaching an extension stem to the artificial joint. The diameter and the length can be adjusted based on size and length of the tibia and the femur. The extension stem is configured to be detachable from a main body and is fixed by twisting and tightening. Often, the extension stem is not formed straightly or the extension stem is attached to a location off-center of the replacement in preparation for a case where bone defects are irregular or bone deformities are severe. This is called off-center or offset.
[0005] Referring to FIGS. 1 and 2 , an offset adapter unit according to prior art is described. The prior adapter unit comprises an adapter 100 and a nut 200 , and the prior adapter 100 includes a head portion 110 being an upper feature and a body portion 120 being a lower feature. The head portion 110 includes a screw groove 111 a having a center axis A 1 . Also, the body portion 120 is eccentric to the head portion 110 and includes a screw portion 122 a having a diameter D and a center axis A 2 . However, there is a problem of increasing pain in patients and risk of reoperation due to a fractured neck 150 caused by repetitive bending moments which occur due to axial loads applied vertically when a common offset is connected and fixed to the femur or tibia.
[0006] (Prior Art) Korean Patent Application Publication No. 10-1989-0019611 Modular Knee Prosthesis System
DETAILED DESCRIPTION
Technical Problem
[0007] The present invention has been made in an effort to solve the problems.
[0008] An object of the present invention is to provide an offset adapter unit which prevents fracture in the narrowest part (neck) by generating an expanded step in a screw connecting region of an adapter for resolving the most vulnerable part to continuously occurring bending moments.
[0009] Another object of the present invention is to provide an offset adapter unit which prevents fracture in the narrowest part (neck) by covering the adapter with a nut having a step.
Technical Solutions
[0010] In order to achieve the above object, the present invention is realized by embodiments having the following features.
[0011] According to one embodiment of the present invention, an offset adapter unit comprises: an adapter which couples a femoral member or a tibial member to a stem member in revision total knee anthroplasty.
[0012] According to another embodiment of the present invention, in the offset adapter unit, the adapter comprises: a head portion; and a body portion.
[0013] According to still another embodiment of the present invention, in the offset adapter unit, the head portion includes a screw groove capable of coupling to the stem member.
[0014] According to still another embodiment of the present invention, in the offset adapter unit, the body portion comprises: an expanded portion and a screw portion.
[0015] According to still another embodiment of the present invention, in the offset adapter unit, the expanded portion forms a step in a direction of the body portion from the head portion.
[0016] According to still another embodiment of the present invention, in the offset adapter unit, the screw portion is formed as a male screw to be coupled to the femoral member or the tibial member.
[0017] According to still another embodiment of the present invention, the offset adapter unit further comprises a nut coupled to the adapter.
[0018] According to still another embodiment of the present invention, in the offset adapter unit, the nut comprises: a step portion and a female screw portion.
[0019] According to still another embodiment of the present invention, in the offset adapter unit, the step portion is coupled to the expanded portion by contact.
[0020] According to still another embodiment of the present invention, in the offset adapter unit, the female screw portion is coupled to a part of the screw portion of the adapter.
Advantageous Effects
[0021] According to the above-described embodiments and the following features, combinations, and relations of use that will be described later, the present invention can obtain the following effects.
[0022] The present invention provides an offset adapter unit which prevents fracture in the narrowest part (neck) by generating an expanded step in a screw connecting region of an adapter for resolving the most vulnerable part to continuously occurring bending moments.
[0023] The present invention provides an offset adapter unit which prevents fracture in the narrowest part (neck) by covering the adapter with a nut having a step.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] FIG. 1 is an engaged perspective view of an offset adapter unit according to prior art;
[0025] FIG. 2 is an engaged section view of the offset adapter unit according to prior art;
[0026] FIG. 3 is an engaged perspective view of an offset adapter unit according to the present invention;
[0027] FIG. 4 is an exploded perspective view of the offset adapter unit according to the present invention;
[0028] FIG. 5 is an engaged sectional view of the offset adapter unit according to the present invention;
[0029] FIG. 6 is a sectional view of the offset adapter unit according to the present invention;
[0030] FIG. 7 is a sectional view of the nut of the offset adapter unit according to the present invention;
[0031] FIG. 8 is an engaged perspective view of a stem member, a femoral member of and the offset adapter unit according to the present invention; and
[0032] FIG. 9 is an engaged perspective view of a stem member, a tibial member and the offset adapter unit according to the present invention.
BEST MODE
[0033] Hereinafter, exemplary embodiments of an offset adapter unit according to the present invention will be described with reference to the accompanying drawings. In describing the present invention, unless not specifically defined, all terminologies in the specification should be interpreted based on the general meanings thereof that a person skilled in the art understands. When the general meanings of the terminologies are incompliant with those used in the specification, the terminologies should be interpreted as being defined herein. Also, well-known functions or constructions will not be described in detail in case they may unnecessarily obscure the understanding of the present invention.
[0034] FIG. 3 is an engaged perspective view of an offset adapter unit according to the present invention; FIG. 4 is an exploded perspective view of an adapter and a nut of the offset adapter unit according to the present invention; FIG. 5 is an engaged sectional view of the offset adapter unit according to the present invention; FIG. 6 is a sectional view of the offset adapter unit according to the present invention; FIG. 7 is a sectional view of the nut of the offset adapter unit according to the present invention; FIG. 8 is an engaged perspective view of a stem member, a femoral member, and the offset adapter unit according to the present invention; and FIG. 9 is an engaged perspective view of a stem member, a tibial member and the offset adapter unit according to the present invention.
[0035] With reference to FIGS. 3 to 9 , the offset adapter unit according to one embodiment of the present invention is described. For resolving a portion which is the most vulnerable to bending moments which continuously occur, the offset adapter unit produces an expanded portion 121 in a screw connecting region of an adapter 1 and a nut 2 having a step portion 21 covers the adapter 1 to prevent fracture of a neck 15 being the narrowest portion.
[0036] Referring to FIGS. 8 to 9 , the offset adapter unit couples a stem member 3 to a femoral member 4 or a tibial member 5 in revision knee arthroplasty and comprises the adapter 1 and the nut 2 .
[0037] Referring to FIG. 4 , the adapter 1 comprises a head portion 11 being an upper structure and a body portion 12 being a lower structure.
[0038] Referring to FIG. 5 , the head portion 11 comprises a screw thread 111 having a center axis A 1 . The screw groove 111 has a female screw thread along an inner circumferential face and the pitch, angle, diameter, number and the like of the thread are formed dependent on a male screw of the stem member 3 .
[0039] Referring to FIGS. 5 and 6 , the body portion 12 is eccentric to the head portion 11 and formed around A 2 as a center axis. The body portion 12 comprises the expanded portion 121 formed by decreasing the diameter of a lower face 112 of the head portion 11 and extending downward; and the screw portion 122 formed by decreasing the diameter of a lower face 121 a of the expanded portion 121 .
[0040] Referring to FIG. 6 , the expanded portion 121 of the diameter D 2 formed by decreasing the diameter of and extending downward from the lower face 112 of the head portion 11 is formed to prevent fracture of the neck 15 vulnerable to the continuously occurring bending moments.
[0041] The screw portion 122 forms a diameter D 1 by decreasing the diameter of the lower face 121 a of the expanded portion 121 and includes a male screw thread in an outer surface of the screw portion 122 .
[0042] Referring to FIGS. 6, 8 and 9 , the screw portion 122 of the adapter 1 is formed as a male screw thread to couple to the femoral member 4 or the tibial member 5 for coupling with the femoral member 4 or the tibial member 5 including a female screw thread. The pitch, angle, diameter, number and the like of the thread of the screw portion 122 are formed dependent on the female screw of the femoral member 4 or the tibial member 5 .
[0043] Referring to FIG. 7 , the outer diameter of the nut 2 is formed by D 4 and the nut 2 includes a penetration hole 20 which penetrates therethrough. In addition, the penetration hole 20 is formed by being surrounded by the step portion 21 which makes contact with the expanded portion 121 of the adapter 1 and the female screw portion 22 coupled to the body portion 12 of the adapter 1 when the nut 2 is fastened to the adapter 1 .
[0044] Referring to FIG. 7 , the step portion 21 is a part which contacts with the expanded portion 121 when the nut 2 is fastened to the adapter 1 . The step portion 21 is formed with an inner diameter of D 3 in an upper portion of the nut 2 . Also, the step portion 21 is configured to prevent fracture of the neck 15 which is the narrowest part by covering the expanded portion 121 of the adapter 1 when the adapter 1 is fastened to the nut 2 .
[0045] Referring to FIG. 7 , the female screw portion 22 is a part which contacts with the screw portion 122 when the adapter 1 is fastened to the nut 2 . The female screw portion 22 is formed in a lower end of the step portion 21 with an inner diameter of D 1 decreased from the step portion 21 . Also, the female screw portion 22 is configured to unite the adapter 1 and the nut 2 when the adapter 1 is fastened to the nut 2 and includes screw threads in an inner circumferential face.
[0046] Referring to FIGS. 6 and 7 , the diameter D 2 of the expanded portion 121 is greater than the diameter D 1 of the screw portion 122 , and the diameter D 1 of the screw portion 122 is approximately the same with the diameter D 2 of the female screw portion. Also, the diameter D 3 of the step portion 21 is greater than or equal to the diameter D 2 of the expanded portion 12 . The outer diameter D 4 of the nut 2 is greater than the diameter D 3 of the step portion 21 . Hence, the diameters are formed to have a relationship of D 4 ≧D 3 ≧D 2 ≧D 1 .
[0047] Referring to FIG. 8 , the femoral member 4 is coupled to the body portion 12 of the adapter 1 and the stem member 3 is coupled to the head portion 11 of the adapter 1 . The femoral member 4 is configured to be fixed by the nut 2 after an axis of the femoral member 4 is adjusted when being fastened to the nut 2 in order to adjust an offset to the femur of a patient.
[0048] Referring to FIG. 9 , the tibial member 5 is coupled to the body portion 12 of the adapter 1 and the stem member 3 is coupled to the head portion 11 of the adapter 1 . The tibial member 5 is configured to be fixed by the nut 2 after an axis of the tibial member 5 is adjusted when being fastened to the nut 2 in order to adjust an offset to the tibial of the patient.
[0049] Referring to FIGS. 2 and 5 , the body portion 120 of the prior adapter 100 extends from the upper portion to the lower portion with a constant diameter D, which causes fracture in the neck 150 subjected to repetitive bending moment due to eccentricity of the axis when being fastened to the nut 200 . On the other hand, according to the present invention, the expanded portion 121 is formed in the adapter 1 , and the overall diameter of the neck 15 being the weak part is made larger by enabling the step portion 21 of the nut 2 to cover the expanded portion 121 . Accordingly, the strength of the adapter unit according to the present invention is greatly improved compared to the prior art.
[0050] In the above, the applicant described preferred embodiments of the present invention. It should be interpreted that such embodiments are merely examples which implement the technical idea and any modification or revision falls within the scope of the prevent invention if it implements the technical idea of the present invention, however. | The present invention relates to an implant playing a role as a joint in coupling a revision implant in revision total knee arthroplasty and, more specifically, to an offset adapter unit comprising an adapter which couples a femoral member or a tibial member to a stem member in revision total knee arthroplasty; and a nut coupled to the adapter, thereby improving the strength by considering fracture occurring in the narrowest area. | 0 |
FIELD OF THE INVENTION
This invention relates to solar collector systems and more particularly to a solar collector unit adapted for connection to a number of other similar units to form an interlocked solar energy collector system where the heated air passes entirely within the individual system units.
Background of the Invention
Solar collector units are well known and consist of an enclosure for the entrapment of air to be heated; a dark (usually black) plate mounted within the box; and a top covering of at least one layer of glass. The space between the glass top and the black plate becomes heated due to the entrapment of the solar energy. The problem with such units as they exist today is that each system must be custom built to fit the particular need. Thus, if it is desired to construct a solar heating system on a roof of a house, a person skilled in construction, usually a carpenter, would be called upon to construct the framework on the roof. This construction would be typically made from wood with a glass covering. This is an expensive and time consuming method of construction and does not lend itself to being built by the typical homeowner. In fact, because of the weight of such systems they typically cannot be used on an existing house, without altering structure.
The solar collectors which come as individual light weight units are also not practical for home use since each unit is typically connected to the next unit by a series of pipes, each pipe being run exterior to the unit. In addition to the construction problems with such an arrangement there is the problem that exterior piping allows for an excessive heat loss which at the same time cuts down on the available surface area available for collecting the solar energy. Also, exterior piping suffers from an inability to carry the volume of air necessary for efficient use of solar energy.
An example of such a modular unit where external piping is used is the F. L. Suhay patent, U.S. Pat. No. 3,399,664 dated Sept. 3, 1968. In Suhay, the solar collector is used to heat water and exterior pipes are used to carry the water between each unit.
Accordingly, a need exists in the art for an easily constructable solar collector system, the individual units of which both provide for solar heating and for the transferring of the heated medium from one unit to the next adjacent unit.
A further need exists in the art for a solar collector unit having internal distribution of the heated medium, each such unit being easily connected to all adjacent units for the purpose of providing a solar collector system utilizing the maximum available surface area.
It is a basic object of my invention to provide for such a solar heating unit which satisfies these requirements while at the same time being light in weight, easily installed, highly efficient and also much cheaper in manufacture and installation.
Summary of the Invention
The above-discussed objects and others are achieved in accordance with one embodiment of my invention where a solar collector unit is constructed as a square box made from a light weight insulating material, such as foamed polyurethane or styrofoam, with a glass top. The top of the box is open and carries at least one pane of glass. Near the bottom of the box there is located a black metal plate. The area between the black plate and the glass top defines a cavity through which the air is to be heated flows. Solar energy is trapped between the glass top and the metal plate in the well-known manner as discussed in U.S. Pat. No. 3,215,134 issued to H. E. Thomason on Nov. 2, 1965, and as discussed in the above-mentioned Suhay patent.
An inlet port is formed in one side wall of the unit and an outlet port is formed in an opposite side wall. Air or any other medium to be heated passes into the unit through the inlet port and moves through the cavity between the metal plate and the top glass surface thereby becoming heated from the available solar energy. The heated air then moves through the outlet port and directly into the inlet port of the next adjacent abutting unit.
The inlet and outlet ports of the units are arranged for interlocking mating relationship with each other such that air seals between adjacent units are easily achievable.
On the side walls which do not contain inlet and outlet ports there are formed mating interlocks so that laterally placed next adjacent units can be interlocked in much the same manner as are adjacent boards in tongue and groove woodwork construction.
Accordingly, it is one feature of my invention to construct a solar heating collector unit having a squareshape with integral input and output ports where the input ports are arranged in mating relationship with the output ports of an adjacent unit.
It is a further feature of my invention that a solar heating collector is arranged so that all of the heated material flows within the units from one unit to the next through integral passages and where the passages are adapted for mating relationship with each other.
It is a further object of my invention to provide a system for the collection of solar energy where the heated medium passes entirely within the individual units of the collector system and where the energy entrapment portion of the system utilizes the maximum available surface area.
DESCRIPTION OF THE DRAWING
These objects and features of my invention, as well as others, will become more fully appreciated from a description of the drawing, in which:
FIG. 1 shows a right side view of the solar collector having the input port on the left and the output port on the right;
FIG. 2 shows a left side view of the same collector shown in FIG. 1 with the input port now on the right and the output port on the left;
FIG. 3 shows a sectional view taken along section 3'3 of FIG. 2; and
FIG. 4 shows in schematic form a system utilizing a number of individual units.
DETAILED DESCRIPTION
As shown in FIG. 1, solar collector unit 10 is arranged in the form of a square within which is carried a glass top surface 31 and a metallic plate 33 which plate is mounted near the bottom of the square. In one side wall 15 of unit 10 an input port 20 is formed having lip 11. In the opposite side wall 17 there is formed an output port 21 having an opening just large enough to accept lip 11 in mating relationship. Air which is forced into unit 10 through port 20 passes between glass surface 31 and metal plate 33 thereby becoming heated from the available solar energy. The heated air is then forced out through port 21 and into a next adjacent unit 10. As will be shown, a number of such units can be interconnected together to form a matrix of units thereby covering the available surface area.
Each unit is also constructed having one side wall 18 with a groove therein and another side wall 16 with a lip 13 adapted to fit into groove 14. Thus, when the units are placed in abutting fashion the unit on the right has its lip 13 in mating relationship with unit 10, groove 14, while unit 10's lip 13 is in mating relationship with groove 13 of the unit next adjacent on the left. Accordingly, all of the units next adjacent unit 10 are mated with unit 10 in an interlocked fashion to form an easily constructable and rigid structure. For added support, an adhesive could be used on the mating parts to prevent any possibility of air leakage or movement. The entire structure can be easily attached to a roof or other surface by a small amount of adhesive under each unit. Since the units are light weight they can be mounted on top of the existing roofing material thereby protectng against water leakage into the building.
In FIG. 2 unit 10 is shown reversed with the input port 20 now on the right and the output port 21 on the left. Of course, it will be noted that the unit works with air flow in either direction and the designation of one port as an input port and one port as an output port is only for convenience of discussion herein.
In FIG. 3 there is shown a cross-section view taken along section 3--3 of FIG. 2. Unit 10 is shown having sides 18 and 16. Side 18 has formed therein groove 14 while side 16 has formed thereon lip 13. The unit has bottom 30 above which is mounted black metal plate 33. Above plate 33 is a glass sheet 32 carried in grooves formed on the interior of unit 10. Above glass sheet 32 is a top glass sheet 31. The purpose of the double glass sheets is to increase the effectiveness of the solar collector by enhancing the entrapment of solar energy. This results since glass is opaque to heat waves, thereby cavity 34 formed between glass sheet 32 and plate 33 becomes heated from the sun's rays. The heated air in unit 10 gives off long rays of energy which do not pass through the glass. The lower layer of glass, sheet 32, provides a barrier to the radiation outward of heat and also acts as a thermal insulator by creating a dead space between glass sheets 31 and 32. However, it should be noted that only a single top sheet of glass or other athermanous mater need be provided. Air to be heated is forced, by a fan (not shown) into input port 11 directly into cavity 34. This air is heated by the energy trapped in cavity 34 and then continues out of the cavity via output port 12 and then directly into the energy cavity of a next adjacent unit. In this manner the air is heated as it passes through the individual units of the system. Since the units abut each other the warmed air is not allowed to cool between units.
In FIG. 4 there is shown an entire system utilizing the concept of my invention. A number of individual units 10 are interconnected together to form a matrix of columns. For purposes of discussion the individual units of the system will be referred to by the intersection point on the grid formed by the rows labeled A-J and the columns labeled 1-8.
Air intake 43 which is located at grid position J8 can be a number of individual units 10 if it is mounted where solar energy is available. Air intake 43 can be constructed in the same manner as unit 10 with input and output ports except that a polystyrene top can be used instead of glass. However, since air intake 43 must pass a large volume of air the input and output ports are ideally made much larger than the regular size input and output ports of unit 10. For use at corners appropriate shapes can be made available, all having internal mating ports for the conducting of air. Distribution units 41 located at grid positions B8 and I8 are each constructed as a solar collector exactly as is unit 10 except that two output ports 21 are provided -- one being larger than the other. One output port (the larger of the two) of unit 41 mates with the large input port of the next adjacent unit 41 and the other (regular size) output port mates with the next adjacent input port of unit 10. For example, looking at unit 41 at position H8 it will be seen that its large input port mates with the large output port of unit 41 at position I8. The larger one of its output ports mates with the large input port of unit 41 at position G8 while the regular size other one of its output ports mates with the input port of unit 10 at position H7.
Unit 40 at corner A8 is constructed having a large input port and a regular size output port on an adjacent side to mate with the units at positions B8 and A7, respectively. Unit 42 at position B1 is constructed having a large and regular size input port and a single large output port. Thus, by combining a number of different types of units, each constructed with internal passages and mating ports, an entire system can be constructed easily and without special tools or ability. By using half-sizes and curved sizes any number of system configurations can be achieved to cover the available surface area. | A modular solar collector unit is arranged for symmetrical connection to other similar collectors to form a solar energy collection system. The individual units are arranged to be interlocked without special tools and without special know-how on the part of the person constructing the system. The units are adapted so that the heated air passes entirely internal to each solar collector unit through mating ports from one unit directly to the next unit. | 8 |
CROSS REFERENCE TO RELATED APPLICATIONS
This Application is a Division of prior application Ser. No. 10/058,325 filed Jan. 30, 2002, which issued as U.S. Pat. No. 6,859,359 on 22 Feb. 2005.
STATEMENT OF GOVERNMENT INTEREST
The invention described herein may be manufactured, used and/or licensed by or for the United States Government.
BACKGROUND OF THE INVENTION
Robotic agents will be ubiquitous on future battlefields, principally to lower the exposure of harm to ground forces. Teams of small collaborating robotic agents, having advanced sensor and mobility characteristics, can be utilized to conduct tasks such as reconnaissance and surveillance, chemical and biological agent detection, logistics, and communications relay. These robotic agents can also be utilized to operate in hostile environments or adverse weather conditions outside of armed forces applications.
Present robotic agents are generally not designed to be used in harsh environments. Current robotic endeavors utilize state of the art components attached to the top of a base with component interfaces and connections (wires) exposed. Additionally, these components are permanently affixed to the base, or embedded into the system, requiring a great deal of time and effort to remove and replace in case of equipment malfunction or system upgrade.
The overall configuration of these robotic agents is not designed to be modular, thereby precluding the use of rapid change components due to replacement due to failure or task changes. Specifically, prior art robotic agents are not water resistant, thermally protected or protected from dust or dirt. Since these agents typically carry sensitive sensors and devices, their lack of protective elements limit their application.
SUMMARY OF THE INVENTION
The present invention overcomes the difficulties of known robotic agents by providing a system which allows the robotic agents unlimited applications in all types of weather and environmental conditions. Furthermore, the present invention provides multiple changes of modular components, thereby providing quick removal of inoperative or damaged parts, as well as allowing for customizing a basic agent for particular use.
It is, therefore, an objective of the present invention to provide a platform system that is quickly attached to vehicular device having a drive train and power supply, where the platform system provides remote data acquisition and transmission.
It is also an objective of the present invention to provide a system for rapid removal, reconfiguration and exchange of components that is easily manipulated and capable of housing a variety of components necessary for information gathering and transmission applications in a wide variety of environmental and weather conditions.
It is also an objective of the present invention to provide a platform system that is capable of being quickly opened so as to allow quick repair, removal, maintenance or upgrade of all apparatus and sensors, all components housed within the platform interior and track all wires connected to each of the apparatus, sensors and components.
It is also an objective of the present invention to provide a platform system that is capable of being opened in a second position to allow direct access to all portions of the robotic components.
It is also an objective of the present invention to provide removable side panels that allow an alternative means of accessing the interiorly housed components and wires as well as effectuating rapid removal of all apparatus, sensors, components and wires.
These and other objectives have led to the present invention discussed below.
DESCRIPTION OF THE FIGURES
FIG. 1 shows a top view of the platform system of the present invention.
FIG. 2 shows a side view of the platform system of the present invention.
FIG. 3 a shows an alternate system access position of the platform system of the present invention.
FIG. 3 b shows an interior configuration of the platform system of the present invention.
FIG. 3 c shows an alternate drive level access position of the platform system of the present invention.
FIG. 3 d shows a rear view of the platform system of the present invention.
FIG. 4 shows the platform system of the present invention positioned on a robotic vehicle.
FIG. 5 shows a top view of the alternate embodiment of the platform system of the present invention.
FIG. 5 a shows a side view of the alternate embodiment of the platform system of the present invention.
FIG. 5 b shows an alternate position of the alternate embodiment of the platform system of the present invention.
FIG. 5 c shows an interior configuration of the alternate embodiment of the platform system of the present invention.
FIG. 6 shows the alternate embodiment of the platform system positioned on a robotic vehicle.
DETAILED DESCRIPTION OF THE EMBODIMENTS
The present invention is directed to a platform system that provides a new and unique manner for housing a plurality of apparatus and sensors storing their respective components and related hardware such that they are rapidly exchangeable, water resistant and capable of operating in a wide range of environmental and weather conditions. The platform system of the present invention is capable of operating as a stationary unit or may be placed upon vehicles having existing robotic units. The modular platform system is capable of accommodating a wide variety of sensors and apparatus for remote data recording, imaging and transmission.
As shown in FIG. 1 , the platform system 1 includes an upper portion 2 , a first side 3 a , a second side 3 b , a front portion 4 and a back portion 5 . The upper portion 2 also includes an outer top surface 6 .
The outer top surface 6 , of the platform system 1 , includes a plurality of plates 6 a , 6 b , 6 c and 6 d that are screwed onto the top surface 6 with screws S. The plurality of plates 6 a , 6 b , 6 c and 6 d are capable of housing several apparatus and sensors, including but not limited to an 8-microphone acoustic array, a visible camera, an infrared camera, a scanning laser rangefinder (LADAR), a point laser rangefinder, 12 sonar sensors, 3 CPUs, 2 wireless LANS, a video transmitter, a GPS sensor, a digital compass, a weather sensor, a stereo camera pair and a driving camera. Additional or alternate plates may be added to the top surface 6 depending upon the number and type of apparatus utilized. Top surface 6 also includes rapid release latch mechanisms 6 e and 6 f that effectuate quick release and closure of upper portion 2 .
The left side view of the platform system 1 , as shown in FIG. 2 , shows a first side 3 a , having air flow apparatus 3 c and 3 d , front portion 4 and back portion 5 . Air flow apparatus 3 c and 3 d include filters, fans and vents that provide necessary air flow to prevent components and wiring of apparatus and sensors positioned on surface 6 , from overheating. The platform system 1 also includes a base portion 7 with sonar sensors 7 a and 7 b . Similarly, second side 3 b includes vents 3 e and 3 f and sonar sensors 7 c and 7 d (not shown).
FIG. 3( a ) shows a preferred embodiment of the present invention. Upper portion 2 is hinged with quick-release hinges 2 a to allow upper portion 2 to be lifted away from front portion 4 and base portion 7 and provide access to interior portion 2 b . To maintain the upper portion 2 at an open position as shown in FIG. 3( a ), a pair of gas-charged lift supports 2 c (proximate to side 3 a ) and 2 d (proximate to side 3 b and not shown) control the rate of ascent to the completed open position. Similarly, gas-charged lift supports 2 c and 2 d also control the rate of descent to prevent inadvertent closing.
As shown in FIG. 3( b ), the hinges 2 a allow the interior portion 2 b to be accessed. The interior portion 2 b of upper portion 2 serves as a housing for wires connecting the devices to their respective power sources and the like. In particular, interior portion 2 b provides a wire housing system W that is used to maintain wire integrity between each apparatus and sensor and their respective components. The wire housing system W effectuates an efficient and rapid manner by which each apparatus' wiring can be easily tracked and identified for rapid maintenance and/or removal. Additionally, wire housing system W also insulates the wiring from sudden jolts and vibrations when the system 1 is in motion. Interior portion 2 b also includes a plurality of brackets B for holding individual components of the devices positioned on surface 6 (the interior portions of panels 6 a , 6 b , 6 c and 6 d , as shown). The brackets B provide additional stability, shock and vibration isolation that prevent sudden jolts and vibration from reaching the components when system 1 is in motion. Note that the positions of the wire housing system W and the brackets B are generally shown in FIG. 3( b ). Exact positioning of these elements will be dependant upon design and functional parameters as understood by one of ordinary skill in the art.
FIG. 3( c ) shows a preferred embodiment of the present invention. Upper portion 2 and base 7 are also configured with quick release hinges 2 d to allow both upper portion 2 and base 7 to be lifted away from front section 4 , and/or removed. This mechanism allows for easy access to all data ports and wiring related to the locomotion including a drive train and power supply of the device. In this configuration, a bottom front portion 8 remains in a stationary position. An interior section 8 a of bottom front portion provides a storage area for additional components or the like.
As shown in FIG. 3( c ), when both upper portion 2 and base 7 are raised, a support mechanism 9 having a catch 9 a and a rod 9 b maintains the upper portion and base in the raised position. A safety cable 9 c will prevent the upper portion 2 and base 7 from opening too far in the ascending direction before 9 a and 9 b can be attached. Quick release latching mechanisms 9 d (proximate to side 3 a ) and 9 e (proximate to side 3 b and not shown) allow for rapidly opening and closing upper portion 2 and base 7 .
FIG. 3( d ) shows the back portion 5 of the system 1 . The back portion 5 includes additional access panels 5 a and 5 b positioned on upper portion 2 . Access panels 5 a and 5 b are screwed into back portion 5 . Alternatively, panels 5 a and 5 b can be hinged and fastened onto back portion 5 using quick release hinges and fasteners. FIG. 3( d ) also shows quick release hinges 2 a that allow for upper portion 2 to be raised, as discussed above. FIG. 3( d ) also shows quick release hinges 2 d which allow upper portion 2 and base 7 to be jointly raised, as discussed above. Back portion 5 also include sonar sensors 5 c and 5 d as well as a recessed interface panel 5 e into which additional apparatus including other robotic mobile units can be connected to pass signal data and power.
FIG. 4 shows a preferred embodiment of the present invention where the platform system 1 is positioned onto and attached to a robotic vehicle, R having a drive train and power supply. First side 3 a provides air flow apparatus 3 c and 3 d (and air flow apparatus 3 e and 3 f on side 3 b , not shown). Front portion 4 includes an aperture 4 a into which a scanning laser rangefinder (LADAR) is positioned. Front portion 4 also includes sonic sensors 4 b . System 1 also allows for a plurality of apparatus and sensors A to be positioned on plates 6 a , 6 b , 6 c and 6 d , as shown. As discussed above, system 1 allows the robotic vehicle R to obtain and transmit data in harsh environments and weather conditions. The platform system 1 provides a water, dust and dirt resistant enclosure mechanism which protects the sensors and apparatus from damage while at the same time providing a mechanism by which individual apparatus/sensor(s), components of the apparatus/sensor(s) including all wiring can be easily accessed, maintained and repaired.
FIG. 5 shows another embodiment of the present invention. As shown, the platform system 101 includes an upper portion 102 , a first side 103 a , a second side 103 b , a front portion 104 , and a back portion 105 . The upper portion 102 also includes an outer top surface 106 .
Outer top surface 106 includes at least two plates 106 a and 106 b that are attached to the surface 106 via screws S. The plates 106 a and 106 b are used to hold a plurality of apparatus and sensors A including but not limited to an 8-microphone acoustic array, a visible camera, an infrared camera, a scanning laser rangefinder (LADAR), a point laser rangefinder, 12 sonar sensors, 3 CPUs, 2 wireless LANS, a video transmitter, a GPS sensor, a digital compass, a weather sensor, a stereo camera pair and a driving camera. Additional and/or alternate plates may be added to the top surface 106 depending upon the number and type of apparatus utilized.
Side portion 103 a includes a side panel 103 c , and side portion 103 b includes a side panel 103 d . Panels 103 c and 103 d are attached to their respective panels via screws S. Additionally, panels 103 c and 103 d may be hinged, utilizing quick release hinges, along the bottom edges (not shown) and fastened using known fastening apparatus. Side panels 103 c and 103 d , as shown in FIG. 5 , also includes air flow apparatus 103 e . Air flow apparatus 103 e include filters, fans and vents to provide necessary air flow to prevent components and wiring from overheating (not shown).
Front portion 104 includes an aperture 104 a for positioning a LADAR within. Additionally, front portion 104 includes front side panels 104 b and 104 c which are attached to front portion 104 via screws S. Back portion 105 includes a panel 105 a which is attached to back portion 105 via screws S and a back dock 105 b . The back dock 105 b provides easy access to other robotic apparatus to board and integrate with system 101 . Alternatively, the back dock 105 b may be replaced with a dispenser for ground sensors, an arm mechanism for retrieving objects, placing objects or performing functions with various arm attachments as will be understood by one of ordinary skill in the art. Alternatively, back dock 105 b may be replaced with a spool for tethering in bad radio frequency environments. Additionally, all of the panels/plates 103 c , 103 d , 104 b , 104 c , 105 a , 106 a and 106 b are removable from system 101 .
FIG. 5( a ) shows the first side portion 103 a with side panel 103 c , removed to provide a quick and efficient manner to access interior portion 102 a . Similarly, FIG. 5( a ) shows front side 104 with front side panel 104 b removed to provide a quick and efficient manner to access interior portion 102 a . Interior portion 102 a houses components and wiring for the apparatus and sensors positioned on surface 106 .
Similar to system 1 , as shown in FIG. 3( b ) (and, therefore not shown), interior portion 102 a provides a wire housing system that is used to maintain wire integrity between each device and their respective components. The wire housing system effectuates an efficient and rapid manner by which each apparatus' wiring can be easily tracked and identified for rapid maintenance and/or removal. Additionally, the wire housing system also insulates the wiring from sudden jolts and vibrations when the system 101 is in motion. Interior portion 102 a also includes a plurality of brackets for holding individual components of the devices positioned on surface 106 . The brackets provide additional stability, shock and vibration isolation that prevent sudden jolts and vibration from reaching the components when system 101 is in motion. Note that the positions of the wire housing system and the brackets are dependant upon design and functional parameters as understood by one of ordinary skill in the art.
FIG. 5( b ) shows another preferred embodiment of the present invention. Upper portion 102 and base 107 are hinged with quick release hinges 102 b to allow both upper portion 102 and base 107 to be lifted. This mechanism allows for easy access to all data ports and wiring related to the robotic devices upon which the system 101 is positioned. In this configuration, front portion 107 a remains in a stationary position. An interior section 107 b of front portion 107 a provides storage areas for component storage or the like.
As shown in FIG. 5( c ), when the upper portion 102 and base 107 are raised, a fastener mechanism 108 , having a catch 108 a and a rod 108 b maintains the upper portion 102 and base 107 in the raised position. A safety cable 108 c prevents the upper portion 102 and base 107 from opening too far in the ascending direction before catch 108 a and rod 108 b are attached. Quick release latching mechanisms 109 a (proximate to side 103 a ) and 109 b (proximate to side) 103 b and not shown allow for rapidly opening and closing upper portion 102 and base 107 .
FIG. 6 shows a preferred embodiment of the present invention where the platform system 101 is positioned and attached onto a robotic vehicle, R having a drive train and a power supply. Front portion 104 includes an aperture 104 a provides a secure area into which a LADAR can be positioned. Front portion 104 also includes removable front side panel 104 b . System 101 provides for a plurality of apparatus and sensors A to be positioned on plates 106 a and 106 b , as shown. System 101 , as discussed above, allows the robotic vehicle R to obtain and transmit data in harsh environments and weather conditions. The platform system 101 provides a water, dust and dirt resistant enclosure mechanism which protects the sensors and apparatus from damage while at the same time providing a mechanism by which individual apparatus/sensor(s), components of the apparatus/sensor(s) including all wiring can be easily accessed, maintained and repaired. | Robot and remote controlled devices have been utilized for information gathering purposes. However these robotic vehicles lack efficiency because they are not capable of operating out of doors or where the sensors and apparatus located on the robots are subject to harsh environments.
The present invention provides a new and unique manner of overcoming these problems by providing a platform system that is placed upon existing robots without requiring adjustments to these devices. The platform effectuates easy installation of a plurality of sensors and apparatus on its top surface while providing internal housing for its wires and components, thereby providing a water, dirt and dust resistant environment which leads to better equipment function and ease of maintenance and repair. | 7 |
FIELD OF THE INVENTION
[0001] The present invention relates to pyrrolo[2,1-c][1,4]benzodiazepine-anthraquinone hybrids useful as potential antitumour agents. The present invention particularly relates to the synthesis of pyrrolo[2,1-c][1,4]benzodiazepine-anthraquinone hybrids as useful anticancer agents. The structural formula of novel pyrrolo[2,1-c][1,4]benzodiazepine-anthraquinone hybrids (V) is as follows, wherein n=3,4; R═H, OH.
[0002] The present invention also relates to a process a process for the preparation of such hybrids and to the use thereof as anti-tumour agents.
BACKGROUND OF THE INVENTION
[0003] Pyrrolo[2,1-c][1,4]benzodiazepines are a family of DNA interactive antitumorur antibiotics derived from streptomyces species. Examples of naturally occurring pyrrolo[2,1-c][1,4] benzodiazepines include anthramycin, tomaymycin, sibiromycin and DC-81. These compounds show their biological activity through covalent binding via their N10-C11 imine/carbinol amine moiety to the C2-amine position of a guanine residue within the minor groove of DNA giving rise to the preference for pu-G-pu sequences. (Kunimoto, S.; Masuda, T.; Kanbayashi, N.; Hamada, M.; Naganawa, H.; Miyamoto, M.; Takeuchi, T and Unezawa, H, J. Antibiot., 1980, 33, 665.; Kohn, K. W. and Speous, C. L. J. Mol. Biol., 1970, 91, 551.; Hurley, L. H.; Gairpla, C. and Zmijewski, M. Biochem. Biophy. Acta., 1977, 475, 521.; Kaplan, D. J. and Hurley, L. H. Biochemistry, 1981, 20, 7572.) The molecules have a right-handed twist, when viewed from the C-ring towards the A-ring. This enables the PBD to mirror the curvature of B-form DNA and maintain isohelical contact with the walls and floor of the minor groove.
[0004] In the last few years a growing interest has been shown in the development of new pyrrolo[2,1-c][1,4]benzodiazepine hybrids. Many PBD conjugates have been synthesized and investigated for their anticancer activity. (Thurston, D. E.; Morris, S. J.; Hartley, J. A. Chem. Commun. 1996, 563.; Damayanthi, Y.; Reddy, B. S. P.; Lown, J. W. J. Org. Chem. 1999, 64, 290; Kamal, A.; Reddy, B. S. N.; Reddy, G. S. K., Ramesh, G Bioorg. Med. Chem. Lett. 2002, 12, 1933). Recently C-8 linked PBD dimers with C2/C2 exounsaturation have been designed and synthesized (Gregson, S. J.; Howard, P. W.; Hartley, J. A.; Brooks, N. A.; Adam, L. J.; Jenkins, T. C.; Kelland, L. R. and Thurston, D. E., J. Med. Chem. 2001, 44, 737).
[0005] Recently, a non cross-linking mixed imine-amide PBD dimers have been synthesized that have significant DNA binding ability and potent antitumor activity (Kamal, A.; Ramesh, G.; Laxman, N.; Ramulu, P.; Srinivas, O.; Neelima, K., Kondapi, A. K.; Srinu, V. B.; Nagarajaram, H. M. J. Med. Chem. 2002, 45, 4679).
OBJECTS OF THE INVENTION
[0006] The main object of the invention is to provide new pyrrolo[2,1-c] [1,4] benzodiazepines useful as anticancer agents.
[0007] Another object of the invention is to provide a process for preparing novel pyrrolo[2,1-c][1,4]benzodiazepines useful as antitumor agents.
SUMMARY OF THE INVENTION
[0008] Accordingly, the present invention provides novel pyrrolo[2,1-c][1,4]benzodiazepine of formula V where n=3, 4 R═H, OH
[0009] In one embodiment of the invention, the compound of formula V is selected from the group consisting of
(a) 7-Methoxy-8-[N-(9,10-dihydro-9,10-dioxo-1-anthracenyl)-propane-3-carboxamide -oxy-(11aS)-1,2,3,11a tetrahydro-5H-pyrrolo[2,1-c][1,4]benzodiazepin-5-one; (b) 7-Methoxy-8-[N-(9,10-dihydro-9,10-dioxo-1-anthracenyl)-propane-3 -carboxamide]-oxy-(4R)-hydroxy-(11aS)-1,2,3,11atetrahydro-5H-pyrrolo[2,1-C][1,4] benzodiazepine-5-one, (c) 7-Methoxy-8-[N-(9,10-dihydro-9,10-dioxo-1-anthracenyl)-butane-4-carboxamide]-oxy-(11aS)-1,2,3,11a tetrahydro-5H-pyrrolo [2,1-c][1,4]benzodiazepin-5-one; and (d) 7-Methoxy-8-[N-(9,10-dihydro-9,10-dioxo-1-anthracenyl)-butane-4-carboxamide]-oxy-(4R)-hydroxy-(11aS)-1,2,3,11a tetrahydro-5H-pyrrolo[2,1-C][1,4]benzodiazepine-5-one.
[0014] The present invention also provides a process for the preparation of pyrrolo[2,1-c][1,4]benzodiazepines of formula V wherein a is 3-4 and R is H, OH,
the process comprising:
reacting N-(9,10-dihydro-9,10-dioxo-1-anthracenyl)-1-bromo-alkanamide of formula I with (2S)-N-[4-hydroxy-5-methoxy-2-nitrobenzoyl]pyrrolidine-2-carboxaldehyde diethyl thioacetal of formula II in an aprotic water miscible organic solvent in the presence of a mild inorganic base
and isolating 2S-N-{4-[N-(9,10-dihydro-9,10-dioxo-1-anthracenyl)-alkane-3-carboxamide]-oxy-5-methoxy-2-nitrobenzoyl} pyrrolidine-2-carbaxaldehyde diethyl thioacetal of formula III so obtained;
[0015] (b) reducing the thioacetal of formula III in presence of organic solvent and isolating 2S-N-{4-[N-(9,10-dihydro-9,10-dioxo-1-anthracenyl)-alkane-3-carboxamide]-oxy-5-methoxy-2-aminobenzoyl}pyrrolidine-2-carbaxaldehyde diethyl thioacetal of formula IV so obtained;
[0016] (c) reacting the amino thioacetal of formula IV with a deprotecting agent to give the pyrrol[2,1-c][1,4]benzodiazepine of formula V wherein n and R are as stated above.
[0017] In one embodiment of the invention, the compound of formula I is reacted with the compound of formula II at refluxing temperature and for a period of 48 h.
[0018] In another embodiment of the invention, the thioacetal of formula III is reduced using SnCl 2 .2H 2 O and in presence of an organic solvent and at reflux temperature.
[0019] In another embodiment of the invention, the organic solvent in step (a) comprises acetone.
[0020] In yet another embodiment of the invention, the base in step (a) comprises K 2 CO 3 .
[0021] In another embodiment of the invention, step (b) is carried out in methanol solvent.
[0022] The present invention also provides a method for the treatment of tumours in a subject, comprising administering to the subject a pharmaceutically effective amount of a pyrrolo[2,1-c](1,4]benzodiazepines of formula V wherein n is 3-4 and R is H, OH,
[0023] In one embodiment of the invention, the subject is a mammal.
[0024] In another embodiment of the invention, the subject is a human being.
[0025] In another embodiment of the invention, the tumour is a human cancer cell line selected from the group consisting of HT-29, HCT-15, A-549, HOP-62 and SiHA.
DETAILED DESCRIPTION OF THE INVENTION
[0026] The present invention provides a novel pyrrolo[2,1-c][1,4]benzodiazepine of formula V wherein n is 3-4 and R is H, OH,
[0027] The precursors, N9,10-dihydro-9,10-dioxo-1-anthracenyl)-1-bromo-alkanamide of formula I (Collier, D. A.; Neidle, S.; J. Med. Chem., 1988, 847) and (2S)-N-[4-hydroxy-5-methoxy-2-nitrobenzoyl]pyrrolidine-2-carboxaldehyde diethyl thio-acetal of formula II (Thurston, D. E.; Murthy, V. S.; Langley, D. R.; Jones, G.; B. Synthesis, 1990, 81) have been prepared by literature methods.
[0028] Some representative compounds of formula V of present invention are given below:
1. 7-Methoxy-8-[N-(9,10-dihydro-9,10-dioxo-1-anthracenyl)-propane-3-carboxamide]-oxy-(11aS)-1,2,3,11a tetrahydro-5H-pyrrolo [2,1-c][1,4]benzodiazepin-5-one 2. 7-Methoxy-8-[N-(9,10-dihydro-9,10-dioxo-1-anthracenyl)-propane-3-carboxamide]-oxy-(4R)-hydroxy-(11aS)-1,2,3,11atetrahydro-5H-pyrrolo[2,1-C][1,4] benzodiazepine-5-one 3. 7-Methoxy-8-[N-(9,10-dihydro-9,10-dioxo-1-anthracenyl)-butane-4-carboxamide]-oxy-(11aS)-1,2,3,11a tetrahydro-5H-pyrrolo [2,1-c][1,4]benzodiazepin-5-one 4. 7-Methoxy-8-[N-(9,10-dihydro-9,10-dioxo-1-anthracenyl)-butane-4-carboxamide]-oxy-(4R)-hydroxy-(11aS)-1,2,3,11a tetrahydro-5H-pyrrolo[2,1-C][1,4] benzodiazepine-5one
[0033] The pyrrolo[2,1-c][1,4]benzodiazepines of formula V wherein n is 3-4 and R is H, OH are prepared by,
reacting N-(9,10-dihydro-9,10-dioxo-1-anthracenyl)-1-bromo-alkanamide of formula I with (2S)-N-[4-hydroxy-5-methoxy-2-nitrobenzoyl]pyrrolidine-2-carboxaldehyde diethyl thioacetal of formula II in an aprotic water miscible organic solvent in the presence of a mild inorganic base
and isolating 2S-N-{4-[N-(9,10-dihydro-9,10-dioxo-1-anthracenyl)-alkane-3-carboxamide]-oxy-5-methoxy-2-nitrobenzoyl} pyrrolidine-2-carbaxaldehyde diethyl thioacetal of formula III so obtained.
[0034] The thioacetal of formula III is reduced with with SnCl 2 .2H 2 O in presence of organic solvent and isolating 2S-N-{4-[N-(9,10-dihydro-9,10-dioxo-1-anthracenyl)-alkane-3-carboxamide]-oxy-5-methoxy-2-aminobenzoyl}pyrrolidine-2-carbaxaldehyde diethyl thioacetal of formula IV so obtained.
[0035] The amino thioacetal of formula IV is reacted with a known deprotecting agent in a conventional manner to give the pyrrol[2,1-c][1,4]benzodiazepine of formula V wherein n and R are as stated above.
[0036] In the process, the compound of formula I is reacted with the compound of formula II at refluxing temperature and for a period of 48 h. The thioacetal of formula III is reduced using SnCl 2 .2H 2 O and in presence of an organic solvent and at reflux temperature. The organic solvent in step (a) of the process is preferably acetone and the base comprises K 2 CO 3 .
[0037] Reduction in step (b) is carried out in methanol solvent.
[0038] The present invention also provides a method for the treatment of tumours in a subject, comprising administering to the subject a pharmaceutically effective amount of a pyrrolo[2,1-c][1,4]benzodiazepines of formula V wherein n is 3-4 and R is H, OH,
[0039] The subject is a mammal such as a human being. The tumour is a human cancer cell line selected from the group consisting of HCT-29, RCT-15, A-549, HOP-62 and SiHA.
[0040] These new analogues of pyrrlo [2,1-c][1,4]benzodiazepine hybrids have shown promising anticancer activity in various cell lines. The molecules synthesized are of immense biological significance with potential sequence selective DNA-binding property. This resulted in design and synthesis of new congeners as shown in scheme-I below wherein:
[0041] The ether linkage is at C-8 position of DC-81 intermediates with Anthraquinone moiety.
[0042] The reaction mixture is refluxed for a period of 24-48 h
[0043] C-8 linked PBD hybrids are synthesised.
[0044] Purification is effected by column chromatography using different solvents like ethyl acetate, hexane, dichloromethane and methanol.
[0045] The following examples are given by way of illustration and therefore should not be construed to the present limit of the scope of invention.
EXAMPLE 1
[0046] To a solution of (2S)-N-[4-hydroxy-5-methoxy-2-nitrobenzoyl]pyrrolidine-2-carboxaldehyde diethyl thioacetal (400 mg, 1 m.mol) of formula II in acetone, anhydrous K 2 CO 3 (553 mg, 4 m.mol) and N-(9,10-dihydro-9,10-dioxo-1-anthracenyl)-1-bromo-propanamide (372 mg, 1 m.mg) of formula I were added and mixture refluxed for 48 h. After completion of reaction K 2 CO 3 was removed by filtration and the solvent was evaporated under reduced pressure, and purified by column chromatography to provide compound III.
[0047] 1 HNMR (CDCl 3 ) 1.21-1.38 (m, 6H), 1.53-2.42 (m, 6H), 2.62-2.81 (m, 6H), 3.10-3.28 (m, 2H), 3.91 (s, 3H), 4.25 (m, 2H), 4.65 (d, 1H), 4.80 (d, 1H), 6.74 (s, 1H), 7.68 (s, 1H), 7.71-7.85 (m, 3H), 8.0 (d, 1H), 8.20-8.30 (m, 2H), 9.15 (d, 1H), 12.38 (bs, 1H).
[0048] To a solution of 2S-N-{4-[N-(9,10-dihydro-9,10-dioxo-1-anthracenyl)-propane-3-carboxamide]-oxy-5-methoxy-2-nitrobenzoyl}pyrrolidine-2-carbaxaldehyde diethyl thioacetal (692 mg, 1 m.mol) of formula III in methanol SnCl 2 .2H 2 O (1128 mg, 5 m.mol) was added and mixture was refluxed till TLC indicated completion of reaction. Methanol was evaporated and 10% NaHCO 3 solution was added. The aqueous layer was extracted with ethyl acetate, the combined organic phases were dried over Na 2 SO 4 and evaporated under vacuum to provide a amino thioacetal (IV) and directly used in the next step.
[0049] A solution of compound IV (662 mg, 1 m.mol) HgCl 2 (624 mg, 2.3 m.mol) and CaCO 3 (250 mg, 2.5 mg) in CH 3 CN—H 2 O (4:1) was stirred at room temperature till TLC indicated complete consumption of starting material. Reaction mixture was diluted with ethyl acetate and filtered through a celite bed. Organic layer was concentrated, dried and purified by column chromatography to give the compound V.
[0050] 1 HNMR (CDCl 3 ) 2.05 (m, 2H), 2.20-2.40 (m, 4H), 2.81 (m, 2H), 3.50-3.81 (m, 3H), 3.91 (s, 3H), 4.15-4.26 (m, 2H), 6.76 (s, 1H), 7.42 (s, 1H), 7.55 (d, 1), 7.80 (m, 3H), 8.0 (d, 1H), 8.2-8.3 (m, 2H), 9.15 (d, 1H), 12.38 (bs, 1H).
EXAMPLE 2
[0051] To a solution of (2S)-N-[4-hydroxy-5-methoxy-2-nitrobenzoyl]pyrrolidine-2-carboxaldehyde diethyl thioacetal (400 mg, 1 m.mol) of formula II in acetone were added anhydrous K 2 CO 3 (553 mg, 4 m.mol) and N-(9,10-dihydro-9,10-dioxo-1-anthracenyl)-1-bromo-butanamide (386 mg, 1 m.mg) of formula I and the mixture was refluxed for 48 h. K 2 CO 3 was removed by filtration and then the solvent was evaporated under reduced pressure, purification by column chromatography afforded compound III.
[0052] 1 HNMR (CDCl 3 ) 1.21-1.42 (a, 6H), 1.60-2.40 (m, 8H), 2.62-2.85 (m, 6H), 3.15-3.30 (m, 2H), 3.95 (s, 3H), 4.10-4.25 (m, 2H), 4.65 (m, 1H), 4.84 (d, 1H), 6.78 (s, 1H), 7.68 (s, 1H), 7.75-7.90 (m, 3H), 8.05 (d, 1H), 8.20-8.35 (m, 2H), 9.15 (d, 1H), 12.38 (bs, 1H).
[0053] To a solution of 2S-N-{4-[N-(9,10-dihydro-9,10-dioxo-1-anthracenyl)-butane-3-carboxamide]-oxy-5-methoxy-2-nitrobenzoyl}pyrrolidine-2-carbaxaldehyde diethyl thioacetal (706 mg, 1 mmol) of formula III in methanol, SnCl 2 .2H 2 O (1128 mg, 5 mmol) was added. The mixture was refluxed till TLC indicated completion of reaction. Methanol was evaporated and 10% NaHCO 3 solution was added. Aqueous layer was extracted with ethyl acetate. Combined organic phases was dried over Na 2 SO 4 and evaporated under vacuum to obtain amino thioacetal (IV) which was directly used in the next step.
[0054] A solution of IV (676 mg, 1 mmol) HgCl 2 (624 mg, 2.3 mmol) and CaCO 3 (250 mg, 2.5 mg) in CH 3 CN—H 2 O (4:1) was stirred at room temperature until the TLC indicated complete loss of the starting material. The reaction mixture was diluted with ethyl acetate and filtered through a celite bed. The organic layer was concentrated, dried and purified by column chromatography to give the compound V.
[0055] 1 HNMR (CDCl 3 ) 1.85-2.40 (m, 8H), 2.60-2.78 (m, 2H), 3.51-3.80 (m, 3H), 3.93 (s, 3H), 4.15-4.20 (m, 2H), 6.78 (s, 1H), 7.42 (s, 1H), 7.60 (d, 1H), 7.65-7.83 (m, 3H), 8.0 (d, 1H), 8.2-8.25 (m, 2H), 9.15 (d, 1H), 12.38 (bs, 1H).
[0000] Biological Activity
[0056] In vitro cytotoxicity against human cancer cell lines: The human cancer cell lines procured from National Cancer Institute, Frederick, U.S.A or National Center for Cell Science; Pune, India. were used in present study. Cells were grown in tissue culture flasks in complete growth medium (RPMI-1640 medium with 2 mM glutamine, 100 μg/ml streptomycin, pH 7.4, sterilized by filtration and supplemented with 10% fetal calf serum and 100 units/ml penicillin before use) at 37° C. in an atmosphere of 5% CO 2 and 90% relative humidity in a carbon dioxide incubator. The cells at subconfluent stage were harvested from the flask by treatment with trypsin (0.5% in PBS containing 0.02% EDTA) for determination of cytotoxicity. Cells with viability of more than 98% as determined by trypan blue exclusion were used for assay. Cell suspension of the required cell density were prepared in complete growth medium with gentamycin (50 μg/ml) for determination of cytotoxicity.
[0057] Stock solutions of (2×10-2 M of test material were prepared in DMSO (Dimethyl sulphoxide). The stock solutions were serially diluted with complete growth medium containing 50 μg/ml of gentamycin to obtain working test solutions of required concentrations.
[0058] In vitro cytotoxicity against human cancer cell lines was determined (Monks, A , Scudiero, D., Skehan, P., Shoemaker R., Paull, K., Vistica, D., Hose, C., Langley, j., Cronise, P., Vaigro-Wolff, A., Gray-Goodrich, M., Campbell, H., Mayo, J and Boyd m.J. Natl. Cancer Inst., 1991, 83, 757-766) using 96-well tissue culture plates. 100 μl of cell suspension was added to each well of the 96-well tissue culture plate. The cells were incubated for 24 hours. Test materials in complete growth medium (100 μl) were added after 24 hours incubation to the wells containing cell suspension. The plates were further incubated for 48 hours (at 37° C. in an atmosphere of 5% and 90% relative humidity in a carbon dioxide incubator) after addition of test material and then the cell growth was stopped by gently layering trichloroacetic acid (TCA, 50 μl, 50%) on top of the medium in all the wells. The plates were incubated at 4° C. for one hour to fix the cells attached to the bottom of the wells. The liquid of all the wells was gently pipetted out and discarded. The plates were washed five times with distilled water to remove TCA, growth medium low molecular weight metabolites, serum proteins etc and air-dried. Cell growth was measured by staining with sulforhodamine B dye (Skehan et al., 1990). The adsorbed dye was dissolved in Tris-Buffer (100 m 1, 0.01M, pH 10.4) and plates were gently stirred for 5 minutes on a mechanical stirrer. The optical density was recorded on ELISA reader at 540 nm.
[0059] The cell growth was calculated by subtracting mean OD value of respective blank from the mean OD value of experimental set. Percent growth in presence of test material was calculated considering the growth in absence of any test material as 100% and in turn percent growth inhibition in presence of test material will be calculated.
[0060] Cytotoxicity: Compounds Va and Vc were evaluated for the primary anticancer activity
TABLE 1 The percentage growth inhibition data for compound Va Concentration Cell lines (mol/L) HT-29 HCT-15 A-549 HOP-62 SiHa 10-6 68 59 47 74 41 10-5 86 66 27 90 52 10-4 93 n.t. 93 n.t. 57
[0061]
TABLE 2
The percentage growth inhibition data for compound Vc
Concentration
Cell lines
(mol/L)
HT-29
HCT-15
A-549
HOP-62
SiHa
10-6
73
61
56
73
40
10-5
87
82
10
97
49
10-4
93
n.t.
93
n.t.
73
n.t. not tested | The present invention relates to synthesis of pyrrolo[2,1-c][1,4]benzodiazepine-anthraquinone hybrids (V) wherein n=3,4; R═H, OH
and to their use as antitumour agents | 2 |
BACKGROUND
[0001] This invention relates to a regenerative drive for piezoelectric transducers.
[0002] Piezoelectric transducers are often employed in the designs of fluidic drop ejectors and in particular, inkjet printers which use piezoelectric drop on demand (DOD) technology. This type of inkjet printer uses a number of print jets, each having an ink-filled chamber in which a piezoelectric element is disposed. Applying a voltage to the piezoelectric element causes the element to deform. The deformation of the piezoelectric element causes a pulse of pressure within the ink filled chamber, forcing expulsion of a drop of ink from the print jet. Applying different types of voltage waveforms to the piezoelectric element can vary the amount and the pattern of the ink expelled from the print jet.
[0003] In conventional inkjet printers, the piezoelectric element is typically driven using a resistive class drive such as a linear amplifier or a rail-to-rail pulser which exhibits power loss in that approximately 10% of the power consumed by the driver is delivered to the piezoelectric element.
SUMMARY
[0004] In a general aspect, a method for regenerative driving of one or more transducers includes, for each of a plurality of driving cycles, enabling one or more of the plurality of transducers for driving, resulting in a number of enabled transducers, configuring a configurable capacitive energy storage element based on the number of enabled transducers and a desired overall capacitance, transferring a predetermined quantity of energy from a power supply to a first inductive energy transfer element, distributing the predetermined quantity of energy from the first inductive energy transfer element, to the configurable capacitive energy storage element and to one or more capacitive energy storage elements of a plurality of capacitive energy storage elements, each energy storage element of the plurality of energy storage elements being coupled to an associated transducer, transferring energy from the one or more capacitive energy storage elements and from the configurable capacitive energy storage element to a second inductive energy transfer element, and transferring energy from the second inductive energy transfer element to the power supply.
[0005] Aspects may include one or more of the following features.
[0006] Transferring the predetermined quantity of energy from the power supply to the first inductive energy transfer element may include transferring the predetermined quantity of energy to a primary winding of a first transformer, distributing the predetermined quantity of energy from the first inductive energy transfer element to the configurable capacitive energy storage element and to the one or more capacitive energy storage elements may include distributing the predetermined quantity of energy from the primary winding of the first transformer, via a secondary winding of the first transformer, transferring the energy from the one or more capacitive energy storage elements and from the configurable capacitive energy storage element to the second inductive energy transfer element may include transferring the energy from the one or more capacitive energy storage elements and from the configurable capacitive energy storage element via a primary winding of a second transformer, and transferring the energy from the second inductive energy storage element to the power supply may include transferring the energy from the primary winding of the second transformer, via a secondary winding of the second transformer, to the power supply.
[0007] The first inductive energy transfer element and the second inductive energy transfer element may be the same element. The configurable capacitor network may include a plurality of selectable capacitors and configuring the configurable capacitive energy storage element may include selecting certain capacitors of the plurality of selectable capacitors based on a set of configuration bits. The method may also include determining the predetermined quantity of energy based on a desired voltage for application to the number of enabled transducers.
[0008] Determining the predetermined quantity of energy and configuring the configurable capacitive energy storage element may be based on a desired rate of change of the desired voltage for application to the number of enabled transducers. Determining the predetermined quantity of energy may include accounting for a history of prior voltages applied to the number of enabled transducers. The first transformer and the second transformer may be flyback transformers operating in discontinuous conduction mode.
[0009] Transferring the predetermined quantity of energy from the power supply to the first inductive energy transfer element may include transferring the predetermined quantity of energy to a first two-terminal inductor and transferring the energy from the second inductive energy storage element to the power supply may include transferring the energy from a second two-terminal inductor to the power supply. The first two-terminal inductor and the second two-terminal inductor may be the same two-terminal inductor. Each of the plurality of transducers may include a piezoelectric element.
[0010] In another general aspect, a system for regenerative driving of one or more transducers includes a plurality of transducers, a configurable capacitive energy storage element, a first inductive energy transfer element, a second inductive energy transfer element, and a controller for operating the system through a plurality of driving cycles. The controller is configured to, for each of the plurality of driving cycles, enable one or more of the plurality of transducers for driving, resulting in a number of enabled transducers, configure the configurable capacitive energy storage element based on the number of enabled transducers and a desired overall capacitance, transfer a predetermined quantity of energy from a power supply to the first inductive energy transfer element, distribute the predetermined quantity of energy from the first inductive energy transfer element, to the configurable capacitive energy storage element and to one or more capacitive energy storage elements of a plurality of capacitive energy storage elements, each energy storage element of the plurality of energy storage elements being coupled to an associated transducer, transfer energy from the one or more capacitive energy storage elements and from the configurable capacitive energy storage element to the second inductive energy transfer element, and transfer energy from the second inductive energy transfer element to the power supply.
[0011] Aspects may include one or more of the following features.
[0012] The first inductive energy transfer element may include a first transformer, the second inductive energy transfer element may include a second transformer, and the controller may be further configured to transfer the predetermined quantity of energy from the power supply a primary winding of the first transformer, distribute the predetermined quantity of energy from the primary winding of the first transformer, via a secondary winding of the first transformer, to the configurable capacitive energy storage element and the one or more capacitive energy storage elements, transfer the energy from the one or more capacitive energy storage elements and from the configurable capacitive energy storage element to a primary winding of the second transformer, and transfer the energy from the primary winding of the second transformer, via a secondary winding of the second transformer, to the power supply.
[0013] The first inductive energy transfer element and the second inductive energy transfer element may be the same element. The configurable capacitor network may include a plurality of selectable capacitors and the controller may be configured to configure the configurable capacitive energy storage element including selecting certain capacitors of the plurality of selectable capacitors based on a set of configuration bits. The controller may be configured to determine the predetermined quantity of energy based on a desired voltage for application to the number of enabled transducers. The controller may be configured to determine the predetermined quantity of energy and configure the configurable capacitive energy storage element based on a desired rate of change of the desired voltage for application to the number of enabled transducers.
[0014] The controller may be configured to determine the predetermined quantity of energy including accounting for a history of prior voltages applied to the number of enabled transducers. The first transformer and the second transformer may be flyback transformers configured to operate in discontinuous conduction mode. The first inductive energy transfer element may include a first two-terminal inductor, the second inductive energy transfer element may include a second two-terminal inductor, and the controller may be configured to transfer the predetermined quantity of energy from the power supply to the first two-terminal inductor and transfer the energy from the second two-terminal inductor to the power supply. The first two-terminal inductor and the second two-terminal inductor may be the same two-terminal inductor. Each of the plurality of transducers may include a piezoelectric element.
[0015] In another aspect, in general, an approach to control of an array of piezoelectric inkjet printheads makes use of an energy transfer approach in which, in each of a series of energizing cycles, energy is first transferred from a power source to an inductor, and then transferred between the inductor and a combination of a selected subset of the printhead's piezoelectric actuator elements and a configurable capacitor, which is configurable according to the selected subset of the actuators, optionally configured further according to states of those actuators prior to the transfer of energy. In some examples, the energy in the actuators and configured capacitors is recovered at the end of the energizing cycle by transferring the energy in the capacitor and the actuators to an inductor (e.g., the same inductor or a second inductor) and then from that inductor back to the power source.
[0016] The combined capacitance of the selected actuators and the configurable capacitance, any initial voltage and/or charge on the actuators, the inductance of the inductor and the current induced on the inductor when it is charged determine both the voltage on the actuators after the energy is transferred as well the rate of change (e.g., a time constant) of the voltage and/or charge during the transition as the energy is transferred from the inductor to the capacitor and actuators. In some examples, the capacitor is configured such that the combination of the actuators and the configurable capacitor provide the same combined capacitance for different numbers of actuators. The current that is induced on the inductor is controlled (for example, by varying the time a supply voltage is applied across the inductor and/or selecting a number of parallel inductors to energize) to determine the voltage that is reached after discharge of the energy from the inductor to the capacitor and selected actuators.
[0017] In some examples, the capacitance of individual actuators, or of printheads in physically local groups, is estimated (e.g., at manufacturing time or in an adaptive manner during operation) so that the capacitance of a selected group of actuators may be known more accurately, and therefore the capacitor can be configured according to the sum of the estimated capacitances of the selected actuators.
[0018] In some examples, non-linear capacitive characteristics and/or hysteresis characteristics of the actuators are accounted for in configuring the capacitance to yield a desired effective capacitance of the configured capacitor and the selected actuators.
[0019] In another aspect, in general, an approach to control of an array of piezoelectric actuators (for example, an array of actuators in a piezoelectric inkjet printhead) makes use of an energy transfer approach in which, in each of a series of energizing cycles, energy is first transferred from a power source to a first energy storage element, and then transferred between the first energy storage device and a combination of a selected subset of the actuators and a second energy storage element. The second energy storage element is configurable according to the selected subset of the actuators, optionally further according to states of those actuators prior to the transfer of energy.
[0020] In some examples, the first storage element comprises an inductor (or more generally, a network of inductors, or even more generally, an element that stores energy in a magnetic field). The second storage element is a configurable capacitor, for example, a digitally controllable capacitor array.
[0021] In some examples, the piezoelectric actuators have capacitive characteristics. More specifically, in some examples, the piezoelectric actuators exhibit non-linear capacitive characteristics and/or hysteresis characteristics.
[0022] The transfer of energy between the first energy storage element and the combination of the selected actuators and the second storage element results a change in energy in the actuators and a change in energy in the second storage element. In some examples, a desired change of state of the selected actuators is associated with a desired change in energy of the actuators. The second storage element is configured according to an energy storage capacity of the second storage element such that substantially all of the energy in the first storage element is transferred to the combination of the configured second storage element and the selected actuators such that the selected actuators reach their final state. In some examples, this desired final state is characterized by a desired final voltage across the selected piezoelectric actuators.
[0023] In some examples, the initial state and/or final state of each of the selected actuators depends on the voltage and/or charge on the actuator. In some examples, the initial state further depends on a prior history of voltage and/or charge, for example, according to a sign of a rate of change of voltage and/or charge.
[0024] In some examples, a desired change of state of the actuators is achieved by one or both of (a) controlling the amount of energy that is stored in the first energy storage element prior to transfer to the second storage element and the selected actuators, and (b) controlling characteristics of the second storage element. For example, controlling the amount of energy in the first energy storage element is accomplished by controlling a time for applying a supply voltage across an inductive first storage element, and/or controlling an inductance of said storage element. Controlling characteristics of the second storage element can, for example, include controlling a total capacitance of said second storage element.
[0025] In some examples, a desired rate of change of state is achieved by one or both of (a) controlling the amount of energy that is stored in the first energy storage element prior to transfer to the second storage element and the selected actuators, and (b) controlling characteristics of the second storage element. In some examples, the rate of change of the state is determined by an electrical time constant determined by characteristics of the first storage element and the combination of the second storage element and the selected actuators. In some examples, a combination of an inductance of the first storage element and a combined capacitance of the configured second storage element and the selected actuators characterizes the electrical time constant.
[0026] Embodiments of the invention may have one or more of the following advantages.
[0027] Among other advantages, driving the piezoelectric elements through an inductance is an intrinsically low-loss method which delivers approximately 95% of the power from the power supply to the piezoelectric elements, limited only by circuit parasitics rather than by circuit topology. Specifically, charging and discharging the print head's load capacitance through dedicated inductors eliminates resistive charging losses and consumes near zero power at idle. Because the print head load capacitance is charged and discharged only through inductors, the only drive circuit losses are due to parasitics—diode voltage drop, transformer winding ESR and leakage inductance losses, and MOSFET switch “on” resistances. This is an improvement over conventional resistive driving methods which may exhibit approximately 90% power loss.
[0028] Other features and advantages of the invention are apparent from the following description, and from the claims.
DESCRIPTION OF DRAWINGS
[0029] FIG. 1 is a piezoelectric drop on demand printing system including a regenerative drive.
[0030] FIG. 2 is a simple example of an energizer and a print head.
[0031] FIG. 3 is a simple timing diagram illustrating the energy transfer between the energizer and print head of FIG. 2 .
[0032] FIG. 4 is a detailed view of the energizer and print head of FIG. 3 , including a number of additional elements.
DESCRIPTION
[0033] Due to the power losses incurred when driving piezoelectric (e.g., “PZT”—lead zirconate titanate) elements using a resistive drive, there is a need for a low-loss driver for piezoelectric elements. The embodiments described herein implement such a low-loss driver by driving and restoring to rest piezoelectric elements using energy transfer through one or more inductive energy transfer elements.
1 OVERVIEW
[0034] Referring to FIG. 1 , a piezoelectric drop on demand (DOD) printing system 100 includes a host 102 (e.g., a general purpose computer), a regenerative drive 104 , and a piezoelectric DOD print head 106 . The regenerative drive 104 includes a power supply 108 , a digital controller 110 (e.g., a microcontroller, an FPGA, or some combination of the two), and an energizer 112 . The energizer 112 includes one or more inductive energy transfer elements 114 (e.g., one or more transformers) and a configurable capacitor 118 . The print head 106 includes a number (e.g., 1024) of “print jets” 116 , each jet 116 including a piezoelectric element which forms a corresponding capacitor.
[0035] Very generally, in operation the host 102 provides print data to the controller 110 of the regenerative drive 104 . The print data includes a specification of which jets 116 of the print head 106 to enable and a specification of a drive voltage waveform to provide to the jets 116 for the purpose of stimulating the piezoelectric elements of the jets. Based on the print data, the controller 110 configures the print head 106 by enabling certain jets 116 , disabling certain other jets 116 and configures the configurable capacitor 118 (as is described in detail below).
[0036] The controller 110 then causes generation of the drive voltage waveform by controlling a timing of charging and discharging of the capacitors of the jets 116 via the inductive energy transfer element(s) 114 . In some examples, to cause generation of the drive voltage waveform the controller 110 first commences a charge phase in which the inductive energy transfer element(s) 114 is briefly connected to the power supply such that a controlled quantity of energy is transferred from the power supply 108 to the inductive energy transfer element(s) 114 where it is stored as magnetic energy in an inductive element (not shown). With the energy stored in the inductive energy transfer element(s) 114 , the controller commences a load phase in which the energy in the inductive element of the inductive energy transfer element(s) 114 is discharged into the capacitors corresponding to the enabled jets 116 and into the configurable capacitor 118 . The load phase results in application of a rising edge of the specified voltage waveform to the piezoelectric elements of the jets 116 .
[0037] After a predetermined amount of time, the controller 110 commences a discharge phase in which the energy stored in the capacitors corresponding to the enabled jets 116 and in the configurable capacitor 118 is transferred back to the inductive energy transfer element(s) 114 where it is stored as magnetic energy in an inductive element. The discharge phase results in application of a falling edge of the specified voltage waveform to the piezoelectric elements of the jets 116 . With the energy stored in the inductive energy transfer element(s) 114 , the controller 110 commences a recapture phase in which the energy stored in the inductive energy transfer element(s) 114 is recaptured by the power supply 108 , accomplishing regeneration.
[0038] Referring to FIG. 2 , one example of the energizer 212 includes two inductive energy transfer elements 214 : a charge transformer 214 a and a discharge transformer 214 b . In some examples, the charge transformer 214 a and the discharge transformer 214 b operate in a manner similar to a standard flyback switching power supply in discontinuous conduction mode.
[0039] As was the case in FIG. 1 , the print head 206 includes a number (i.e., N) of jets 216 , each including a corresponding piezoelectric capacitor 217 (C 1 . . . C N ) and connected in parallel to a configurable capacitor 218 (C C ) (e.g., a 10-bit programmable capacitance network).
1.1 Inductive Energy Transfer Elements
[0040] The charge transformer 214 a includes two windings: a primary winding L 1,1 and a secondary winding L 1,2 which are wound around a common core. Any voltages present on the primary and secondary windings are in phase and any currents present on the primary and secondary windings are 180° out of phase. The charge transformer 214 a also includes a charge switch 220 (e.g., a field effect transistor (FET) switch) disposed between its primary winding L 1,1 and ground. In general the charge transformer 214 a is used to generate the rising edge(s) of the drive voltage waveform.
[0041] The discharge transformer 214 b includes two windings (i.e., inductors): a primary winding L 2,1 and a secondary winding L 2,2 which are wound around a common core. As is the case with the charge transformer 214 a , any voltages present on the primary and secondary windings are in phase and any currents present on the primary and secondary windings are 180° out of phase. The discharge transformer 214 b also includes a discharge switch 222 (e.g., a FET switch) disposed between its primary winding L 2,1 and ground, a DC blocking diode 241 (to block DC current flow through the secondary winding L 2,2 ), and a commutation diode 243 . In general the discharge transformer 214 b is used to generate the falling edge(s) of the drive voltage waveform.
1.2 Print Jets
[0042] Each jet 216 of the print head 206 and its corresponding piezoelectric capacitor 217 is connected in parallel to both the charge transformer 214 a and the discharge transformer 214 b through a jet toggle switch 224 . In some examples, the jet toggle switches 224 are implemented as FET devices within ASIC(s). In some examples, the print head 206 includes many jets, for example, in the range of 128 to 4096, with the same number of corresponding piezoelectric capacitances and associated switches. In some examples, the individual piezoelectric capacitances are in the range of 50 pF to 1 nF.
1.3 Configurable Capacitor
[0043] The configurable capacitor 218 is connected to both the charge transformer 214 a and the discharge transformer 214 b , and is connected in parallel to the piezoelectric capacitors 217 of the jets 216 . As is noted above, in some examples the configurable capacitor 218 is a 10-bit capacitor network which is capable of being configured within a range of capacitances which encompasses a worst case capacitance of the print head 206 when operating at a maximum intended temperature (i.e., a point of maximum jet capacitance). In some examples, the ten control bits of the configurable capacitor 218 are divided functionally into a three-bit coarse valued network, a three-bit mid valued network, a three-bit fine valued network, and a final smallest capacitor. The mid value, fine value, and smallest networks have a capacitance which is about 40% greater than a standard binary progression to allow for capacitor tolerance variations. In some examples, each of the three-bit networks has a guaranteed monotonic operation but the individual networks do not match well to form a single 10-bit monotonic binary network.
[0044] The effective capacitance of the configurable capacitor 218 is measured during fabrication at each of the 10-bit control values using an external capacitance meter with a few volts of DC bias setting. The table of 1024 (i.e., 2 10 ) resulting capacitance values is then sorted by an external algorithm. The algorithm selects a subset of capacitance values from this list (e.g. 512 values) which represent a best fit straight line to a linear capacitance progression ranging from a maximum capacitance value (i.e., all bits on) to a minimum capacitance value (i.e., all bits off). Due to the tolerances of the capacitors used in the configurable capacitor 218 and available component choices, the fit to a straight line is generally imperfect. In some examples, codes appear out-of-order and some may even be duplicated. In some examples, the table of capacitance values has a precision in the range of an 8.4-8.8 bit capable configurable capacitor 218 , depending on individual capacitor tolerance. However, in some examples, the configurable capacitor 218 includes approximately 40% extra total capacitance range to allow for print head capacitance variation at manufacture and with temperature. This extra capacitance range reduces the usable precision of the configurable capacitor 218 to approximately 7.9-8.3 bits. In some examples, the configurable capacitor 218 has better than 1% adjustability within its working range.
[0045] In some examples, all of the capacitors used in the configurable capacitor besides the smallest capacitor are polyethylene naphthalate (PEN) film type capacitors. PEN film type capacitors track each other well with temperature variation, eliminating a need to re-linearize the configurable capacitor 218 due to temperature variation. In other examples, temperature-compensated capacitors (NPO/COG) are used. In some examples, the individual elements of configurable capacitor 218 are located in a vicinity of each other to ensure that they are at similar temperatures.
[0046] In some examples, a table of 512 10-bit configuration codes for the configurable capacitor is generated from the straight line capacitance fit described above. The table is provided to the controller 110 which stores the table for future use as a linearization table for the configurable capacitor. The maximum capacitance value of the configurable capacitor 218 (i.e., the capacitance value when all 10 bits of the configuration code are set to 1) is also provided to and stored by the controller as a factory measured constant referred to as “ConfigMaximum” (in nF). ConfigMaximum is used to accurately report the measured equivalent capacitance of the print head 206 , at a chosen voltage state, to the host 102 .
2 OPERATIONAL DETAIL
[0047] In general, the energizer 212 and the print head 206 are operated by the controller 110 such that the energizer 212 provides a waveform including a series of pulses having shapes specified by the host 102 to the print head 206 . In some examples, for each pulse, the energizer 212 and print head 216 are cycled through an initialization phase (I) and five energy transfer phases which are labeled (1)-(5) in FIG. 2 . In other examples where more complex, composite pulse shapes (e.g., a short trapezoid on top of a longer trapezoid) are used, more than five phases per pulse are required.
[0048] In the initialization phase, the controller 110 receives an encode trigger 356 from an encoder (not shown) indicating a print request from the host 102 . The controller 110 subsequently sends a command to the print head 206 which causes a first subset of jets 216 to be enabled (i.e., to have their jet toggle switches 224 closed) and causes a second subset of the jets 216 to be disabled (i.e., to have their jet toggle switches 224 opened). In some examples, the command from the controller 110 is based on print data received from the host 102 .
[0049] Since each of the jets 216 has a corresponding piezoelectric capacitor 217 , enabling different numbers of jets 216 causes the overall capacitance connected to the inductive charge transfer element(s) 214 due to the jets 216 to vary. Without compensating for this varying capacitance, the drive voltage waveform provided to the jets 216 would deviate from the desired drive voltage waveform specified by the print data. For example, the slew rate of the drive voltage waveform and the final voltage of the drive voltage waveform may deviate from a desired slew rate and a desired voltage. To compensate for the varying capacitance presented by the jets 216 , the configurable capacitor 218 is connected in parallel to the piezoelectric capacitors 217 of the jets 216 . In general, for each pulse in the drive voltage waveform, the configurable capacitor 218 is configured such that the sum of the capacitance of the enabled jets 216 and the capacitance of the configurable capacitor 218 is maintained at an approximately constant capacitance value regardless of the number of enabled jets 216 .
[0050] To configure the configurable capacitor 218 the controller 110 calculates a 9-bit address lookup into the table of 512 10-bit configurable capacitor configuration codes and uses the address to retrieve the 10-bit configuration code corresponding to the address. The 10-bit configuration code is applied to a control line of the configurable capacitor 218 whereby the capacitance of the configurable capacitor 218 is configured. In some examples, the address calculated by the controller 110 has different number of bits based on the number of elements in the table (e.g., 10 bits for 1024 elements or 8 bits for 256 elements).
[0051] The controller 110 dynamically calculates the 9-bit address lookup for each pulse of the waveform using the equation:
[0000] ConfigAddress=ConfigCoefficient*(NumJets−NumEnabledJets)
[0000] where NumJets is the total number of jets 216 included in the print head 206 and NumEnabledJets is the number of jets 216 that are enabled for the current pulse. ConfigCoefficient depends on the particular print head 206 and configurable capacitor 218 . For NumJets=1024, for a typical printhead and corresponding circuit design, ConfigCoefficient ranges from a typical value of approximately 330/1024 up to a maximum value of 511/1024. In general, ConfigCoefficient controls the amount of the total range of the configurable capacitor 218 that is used to compensate for varying print head jet capacitance.
[0052] The controller 110 initially calculates the ConfigCoefficient value based on system power-up self-calibration trials. The ConfigCoefficient value is periodically (e.g., during each initialization phase) adjusted during operation such that the capacitance of the configurable capacitor 218 when zero print head jets 216 are enabled is approximately equal to the sum of the capacitance of jets 216 when all of the jets 216 are enabled.
[0053] The ConfigAddress is calculated for each pulse of the drive voltage waveform according to the above equation. Mapping ConfigAddress through the capacitance linearization table to the configurable capacitor 218 causes the configurable capacitor 218 to add an appropriate amount of capacitance to the overall print head capacitance, C total (i.e., the sum of the enabled jet capacitance and the configurable capacitor capacitance), thereby maintaining a generally-constant overall load capacitance. In some examples, in order to optimize fluid jetting the overall load capacitance is allowed to deviate from the generally constant capacitance. In practice, since the capacitances associated with the jets 216 vary with applied voltage, a constant overall capacitance may only be achieved at one or two points during the generation of the drive waveform.
[0054] In some examples, the control lines of the configurable capacitor 218 are updated by the controller 110 simultaneously with the controller 110 enabling and disabling the individual jets 216 of the print head 206 . In some examples, since the table of configuration codes for the configurable capacitor 218 is linearized, a side effect of calculating ConfigCoefficient is that the print head's effective capacitance with all jets 216 enabled is equal to the capacitance value calculated by the equation: ConfigMaximum*ConfigCoefficient*NumJets. This capacitance value may be reported by the system to the host 102 for diagnostic and experimental purposes.
[0055] Continuing to refer to FIG. 2 and also referring to FIG. 3 , with the jets 216 enabled and the configurable capacitor 218 configured, the controller 110 commences a first stage (1) in which energy is transferred from the power supply 108 to the charge transformer 214 a . In the first stage, the controller 110 provides a controllable width charge command pulse 324 to the charge switch 220 , causing the charge switch 220 to close for a controllable time interval.
[0056] While the charge switch 220 is closed, the current in the primary winding L 1,1 of the charge transformer 214 a rises in a linear manner at a rate determined by the power supply voltage V CC divided by the inductance, L, of the primary winding of the charge transformer 214 a as follows:
[0000]
I
(
t
)
=
t
V
CC
L
[0057] The linear rise of the current in the charge transformer's primary winding represents an amount of stored energy growing in time with the square of the length of the charge command pulse 324 :
[0000]
E
(
t
)
=
1
2
LI
(
t
)
2
=
1
2
L
V
CC
2
t
2
[0058] While the current in the charge transformer's primary winding is increasing, a charging diode 232 prevents formation of an opposing current in the charge transformer's secondary winding.
[0059] At the falling edge of the charge command pulse 324 a second phase (2) commences in which the charge switch 220 opens and the energy stored in the primary winding L 1,1 of the charge transformer 214 a is transferred through the secondary winding L 1,2 of the charge transformer 214 a and the diode 232 into the capacitors of the combined capacitive load of the print head 206 (i.e., the piezoelectric capacitors 217 of the enabled jets 216 ) and the configurable capacitor 218 . The transfer of energy into the combined load causes the voltages on the piezoelectric capacitors 217 of the enabled jets 216 to rise in the form of the first quarter-cycle of a quasi-sine wave 328 . The current on the secondary winding L 1,2 of the charge transformer 214 a simultaneously declines in the form of a first quarter-cycle of a quasi-cosine wave 330 (both waveforms are only quasi-sine or cosine, rather than pure sine or cosine, due to the nonlinear charge-to-voltage characteristics of the jet effective capacitance). If the piezoelectric capacitors 217 of the enabled jets 216 and the configurable capacitor 218 are linear, the fundamental period of the rising edge of the voltage waveform 328 (and the falling edge of the current on the secondary winding L 1,2 of the charge transformer 214 a ) is 2π√{square root over (LC total )} where L is the charge transformer's inductance (e.g., 35 uH) and C total is the combined capacitance of the print head 206 and configurable capacitor 218 .
[0060] The energy which was stored in the primary winding of the charge transformer 214 a is nearly completely transferred to the capacitors 217 , 218 , resulting in a total energy of (½)C total V 2 being stored on the capacitors 217 , 218 .
[0061] Since the above-described charge event adds a controlled amount of energy to the capacitors 216 , 217 of the print head 206 , the charge command pulse width calculation must take the starting voltage of the capacitors 216 , 217 into account. From an initial voltage V 0 , production of a final voltage V 1 requires a charge command pulse of length T CHARGE :
[0000]
T
CHARGE
=
LC
total
V
1
2
-
V
0
2
V
CC
[0000] where, neglecting component parasitic losses, V CC is the power supply voltage, L is the inductance of the primary winding of the charge transformer 214 a and C total is the effective print head capacitance plus configurable capacitor capacitance.
[0062] Rescaling time in terms of clock cycles of the controller 110 gives:
[0000]
N
CHARGE
=
F
CLOCK
LC
total
V
1
2
-
V
0
2
V
CC
[0000] where N CHARGE is the charge command pulse length measured in clock cycles of the controller, and F CLOCK is the controller's clock frequency (e.g., 62.5 MHz). In some examples, the peak voltage attained on the piezoelectric capacitors 217 , when starting from zero volts, is roughly 20 volts per microsecond of charge time.
[0063] In some examples, the effective capacitance of the print head 206 changes with fire pulse target voltage and also separately with voltage history (i.e., the magnitude and direction of prior charge and discharge operations for each jet 216 ). In particular, jet 216 may have a different on/off history through the progress of a multi-pulsed grayscale waveform.
[0064] To accommodate the capacitance variation of the jets with voltage, for every charging event in the original voltage waveform specification, the controller 110 calculates an amount of energy E CC (v) required to charge the chosen maximum capacitance of the configurable capacitor 218 to the desired final voltage V, and separately calculates the energy E JETS (v) required to charge the print head's all-on jets capacitance to the same final voltage. During printing, the two energy values are scaled in the controller 110 by an instantaneous “enabled” jet count fraction, and summed as follows:
[0000] E TOT =DE JETS +(1− D ) E CC
[0000] where E TOT is the total required charge energy and D is the instantaneous jet “enabled” fraction (i.e., the count of currently enabled jets in the print head divided by the total number of jets in the print head; a real number ranging from 0 to 1). The term (1−D) is used to compute a complementary portion of the chosen maximum capacitance of the configurable capacitor to achieve an energy input requirement for this charging event which is approximately independent of the number of jets enabled at the charging event.
[0065] The controller 110 then calculates the required charge command pulse length in system clock periods as follows:
[0000] N CHARGE =F CLOCK √{square root over (2 LE TOT )}/ V CC
[0066] To reduce controller hardware resource requirements and to scale to integer values, the controller 110 calculates scaled quantities P JETS and P CC from E JETS and E CC :
[0000] P JETS =E JETS F CLOCK 2 2 L
[0000] P CC =E CC F CLOCK 2 2 L.
[0000] The controller then calculates:
[0000] P TOT =DP JETS +(1− D ) P CC
[0067] The controller 110 then calculates the charge command pulse length (in system clock cycles) as:
[0000] N CHARGE =√{square root over ( P TOT )}/ V CC
[0068] In general, the above total energy calculations work well for non-grayscale drive voltage waveforms, or grayscale drive voltage waveforms which have relatively uniform pulse voltages so that the voltage history for each jet 216 is similar and can be compensated for during the microcontroller's calculation of the single value E JETS .
[0069] In some examples, when different jets have different voltage histories, an extension of the preceding total energy calculation is used. In particular, the previously described nonzero gray-level setting of each jet 216 is stored by the controller 110 and is used along with the current gray level of each jet. The previous nonzero and current gray levels together (4 discrete levels or 2 bits each for example) determine the energy requirement for a given jet at each charge command pulse.
[0070] In one example, there are 4×4=16 possibilities for combined current and previous voltage histories. The total number (i.e., count) of jets which belong to each of the sixteen voltage history groups are calculated into 16 jet history count buckets. A table, filled by the controller 110 , lists the amount of charge energy required for a jet 216 to reach the target voltage for each of the 16 voltage history possibilities. The 16 required charge energies in the table are individually multiplied (i.e., weighted) by the number of jets 216 which belong to their corresponding history group (i.e., the count in each of the 16 history buckets), and the results of the multiplications are summed to a weighted total energy. The weighted total jet energy plus the energy required to charge a complementary portion of the configurable capacitor to the same target voltage is used as the required charge energy for the print head (i.e., E TOT ) for the current charge cycle. The count in each of the 16 history buckets of jet history is stored by the controller charge transfer cycle for future readback as a data point for analysis by the controller 110 .
[0071] In some examples, if the drive voltage waveform shape does not include a specialized pulse which is supplied to all jets at a printed gray level of zero (e.g., a Meniscus Control or Tickle pulse), then the last nonzero gray level for each jet is stored rather than the last gray level, since zero gray level pulses do not modify the jet's voltage history.
[0072] In some examples, groups of piezoelectric capacitors 217 in different locations on the print head 216 have differing charge-to-voltage properties. In such examples, a bucket of counts of energized jets can be maintained for each group of piezoelectric capacitors 217 . A required amount of energy can then be calculated for each group rather than for individual jets.
[0073] In some examples, typical charge command pulse lengths are in a range around a nominal value of 6 microseconds (about 384 system clocks) to create a 130 v drive pulse, depending on 48 v supply voltage, component tolerances, and actual print head capacitance at the operating temperature.
[0074] In some examples, rather than calculating a charge command pulse length to achieve a certain energy level (and a certain peak current) in the first energy storage element, a calculation of a desired peak current may first be made for the first energy storage element. The first energy storage element is then charged through a current-sensing circuit to that controlled peak current.
[0075] In some examples, it is important that the actual jet excitation voltage (the leading edge of the drive voltage waveform's trapezoid pulse) starts very soon after the host printing system's writing encoder trigger 356 , or a fixed delay time after the encoder trigger 356 , or preferably a variable adjustment period after the encoder trigger 356 which automatically adjusts in length with encoder period (e.g., a constant sub-pixel delay). Since the drive voltage waveform starts to rise only after the end of the charge command pulse, and the charge command pulse is of variable length, the drive voltage waveform can not start immediately after the encoder trigger 356 . Instead, the start of the drive voltage waveform is delayed a fixed amount of time by control logic, or preferably a fixed sub pixel delay time which automatically scales with printing speed (i.e., a fixed fraction of the writing encoder period). The first charge command pulse is scheduled by control logic to end at the end of the delay period to start the drive voltage waveform transitions at the proper time. This delay period is longer than the longest anticipated charge command pulse including all tolerances. In some examples, the delay period is longer than 9 microseconds.
[0076] In a third phase (3), the peak voltage 334 remains stored on the print head capacitance 217 and configurable capacitor 218 until a discharge event occurs.
[0077] After a predetermined amount of time, the controller 110 commences a fourth charge transfer stage (4) in which the peak voltage 334 on the piezoelectric capacitors 217 of the jets 216 and the configurable capacitor 218 is discharged using the discharge transformer 214 b . This discharge of voltage into the discharge transformer 214 b causes a falling edge 336 in the drive voltage waveform.
[0078] To begin the fourth charge transfer stage, the controller 110 issues a discharge command pulse 338 of controllable width to the discharge switch 222 of the discharge transformer 214 b , causing the discharge switch 222 to close. When the discharge switch 222 closes, the voltage on the capacitors 217 , 218 declines toward zero volts in the form of the first quarter-cycle of a quasi-cosine wave. The current in the primary winding L 2,1 of the discharge transformer 214 b simultaneously rises in the form of the first quarter-cycle of a quasi-sine wave 340 . For an ideal (i.e., linear) total print head capacitance, the fundamental period of both the falling print head capacitor voltage and the rising primary winding current is 2π√{square root over (LC total )} where L is the inductance of the primary winding of the discharge transformer 214 b (e.g., 35 uH) and C total is the total capacitance of the print head (e.g., about 145 pF*1024 jets). In some examples, the period is approximately 14 microseconds depending on print head parameters, temperature and component tolerances. The actual falling edge duration is one-quarter of that full period.
[0079] In some examples, not all of the voltage stored on the capacitors 217 , 218 is discharged. For example, For an ideal print head capacitance, the actual final voltage V 1 may be expressed as a function of initial voltage V 0 and discharge command pulse length t (in seconds):
[0000]
V
1
=
V
0
cos
(
t
LC
)
[0080] Solving for discharge command pulse length t (seconds):
[0000]
t
=
LC
arccos
(
V
1
V
0
)
[0081] Rescaling time in terms of system clock periods gives:
[0000]
Q
D
=
F
C
LC
arccos
(
V
1
V
0
)
[0000] where Q D is the discharge command pulse length measured in system clock periods, and F C is the system clock frequency (e.g., 62.5 MHz).
[0082] In some examples where the voltage on the capacitors 217 , 218 is completely discharged, once the voltage has fallen past zero volts, a commutation diode 243 connected across the capacitors 217 , 218 begins to conduct and maintains the current accumulated on the discharge transformer's primary winding, clamping the voltage on the capacitors 217 , 218 to near zero until the discharge switch 222 is opened. In general, the commutation diode 243 allows the discharge switch 222 to be opened at a time after the voltage of the capacitors 217 , 218 has reached zero volts rather than requiring that the discharge switch 222 is opened exactly when the voltage of the capacitors 217 , 218 equals zero volts. In this way, the commutation diode 243 simplifies the timing requirements for the discharge switch 222 . In some examples, commutation diode 243 is not included in the energizer circuit 212 .
[0083] At the end of the discharge command pulse 338 , the energy stored in the primary winding of the discharge transformer 214 b is transferred back into the power supply 108 via the secondary winding L 2,2 of the discharge transformer 214 b in the form of a linear ramp down to zero current 344 . Due to the presence of the commutation diode 243 , the discharge command pulse 338 width may be a fixed duration if the goal is to always discharge the capacitors 217 , 218 to zero volts (i.e., such a discharge takes a fixed amount of time regardless of the starting voltage, and in practice the discharge command pulse 338 may have a duration fixed at, for example, 20% longer than a quarter of the approximate 14 microsecond fundamental period to allow for tolerances).
[0084] In some examples, the PZT capacitances associated with the jets 216 vary with applied voltage and voltage history, so the above equations are an approximation.
3 ADDITIONAL FEATURES
[0085] Referring to FIG. 4 , a more detailed diagram of the energizer 412 and the print head 406 includes a power supply filter 448 , a power supply analog to digital converter (ADC) 446 , a print head voltage ADC 452 , and an overvoltage detector 450 .
[0086] The power supply filter 448 receives input from the power supply 108 and applies a filter (e.g., an analog L-C low pass filter) to limit the rate of voltage variation presented to the energizer 412 , present a well-controlled and damped impedance to the energizer 412 , and serve as a reservoir for charge and discharge current pulses, attenuating them before they exit the energizer 412 through the power supply cabling. The characteristic of the power supply filter 448 depends on the equivalent series resistance provided by its series inductor and fuse to damp the resulting L-C-R network response. Input power to the energizer 412 is limited (e.g., less than 250 mA DC may be consumed under any printing circumstance), so the filter inductance is physically quite small. In one example, five 22 uF 63 v ceramic capacitors may be used.
[0087] The power supply ADC 446 and the print head voltage ADC 452 are included to allow for accommodation of power supply variation in real time, self-calibration for print head and component tolerances, and drift of print head capacitance with temperature. In some examples, due to the need for real-time measurement, ADC total aperture and conversion time of one microsecond or less is required.
[0088] The power supply ADC 446 measures the voltage of the power supply 108 coming out of the power supply filter 448 immediately before each charge command pulse is generated. The measured voltage is used to compensate (e.g., in hardware) the subsequent charge command pulse length for the effects of power supply variation. It is important to measure the instantaneous power supply voltage just before each charge command pulse is generated since the measured voltage and the power supply input filter's frequency response together provide the only immunity to power supply voltage variation. The power supply voltage readings from this ADC are also compared against upper and lower voltage limits by the controller 110 . The controller uses the result of the comparison to signal a supply voltage out-of-range error to the host 102 .
[0089] In some examples, each reading from the power supply ADC 446 is stored in a dedicated hardware register in the controller. The register can be read for the purpose of reporting the power supply voltage to the host 102 .
[0090] In some examples, the controller 110 includes a voltage compensation table which is indexed using possible values of the power supply voltage. The power supply voltage stored in the register can be supplied to the compensation table to retrieve a compensation value. The compensation value is the inverse of its address in the compensation table at every entry (i.e., 1/PowerSupplyVoltage). The compensation value is provided to a multiplier which performs a final adjustment to the charge command pulse width to null out the effect of changing power supply voltage, since the desired charge command pulse length varies inversely with power supply voltage.
[0091] In some examples, an ADC may be used to directly measure the peak current achieved in the first storage element for later use by the controller 110 to calculate and predict optimum charge control timing values for subsequent operations.
[0092] The print head voltage ADC 452 measures the instantaneous voltage stored on the combined load of the print head and configurable capacitors 417 , 418 after each charge and discharge event. The print head voltage ADC measures drive pulse amplitudes as the drive voltage waveform progresses in real time for software self-calibration of the energizer 412 . Besides its main use for tuning of the energizer 412 , the print head voltage ADC 452 also allows real-time detection of unexpected load conditions (e.g., a missing print head, or a printhead containing defective (short-circuited or open-circuited) piezoelectric capacitors which could result in the calculated ConfigCoefficient value falling outside of a permissible range or changing too rapidly.
[0093] In some examples, the print head voltage ADC 452 takes readings before each charge command pulse begins, just before each charge command pulse ends, just before each subsequent discharge command pulse begins, and just after each subsequent discharge command pulse ends for each drive pulse. In some examples, the readings are stored in a FIFO stack along with the jet “enabled” count (for 1-bit operation) or 16-bucket jet history counts (for 2-bit grayscale operation) for later read-back and regression analysis by the controller 110 .
[0094] In some examples, the controller 110 uses the stored measurement results to periodically recalculate and adjust the working estimate of the ConfigCoefficient variable and the charge energy to voltage curves for the jet capacitances 217 and the configurable capacitance 218 . In some examples, if the controller 110 can not keep up with the actual firing frequency of the drive voltage waveform, regression analysis is performed on a sampling of the waveform data. For example, the waveform data is sampled periodically to gather data points which represent printing with many print head jets enabled and few print head jets enabled over the range of possible drive waveform voltages and voltage histories. This allows the controller 110 to extract separate charge energy requirements for the configurable capacitor's ordinary capacitance and for the nonlinear effective capacitance of the jets 216 at the waveform voltages in use at the time.
[0095] The overvoltage detector 450 limits the maximum peak voltage supplied to the print head 406 under fault conditions to avoid damaging the print head 406 . In some examples, the voltage is limited to approximately 150 volts. In some examples, the overvoltage detector 450 includes an NPN transistor which signals the controller 110 when an output overvoltage has been detected. The controller 110 latches this error and shuts the energizer 412 down by ceasing issuance of charge command pulses.
[0096] In some examples, since the effective capacitance of the jets of the print head varies with voltage and voltage history, but the configurable capacitor's capacitance does not, the practice of “matching” the configurable capacitance against the effective capacitance of the jets of the print head is not straightforward. In some examples, a value of ConfigCoefficient may be chosen to match energy input to jets of the print head and the configurable capacitor at a specific voltage and history point (e.g. to charge from 0 to 100V after a recent discharge from 100V to 0V). Alternatively, ConfigCoefficient may also be chosen to have the configurable capacitor 218 charge/discharge time constant match either the print head capacitance charge or discharge time constant, but generally not both. Instead, through jetting characterization, the value of ConfigCoefficient would be chosen to stabilize jetting characteristics, maintaining constant drop volume and time of flight with varying print head energized jet count.
4 ALTERNATIVES
[0097] In some examples, the inductive energy transfer element 114 may include only a single transformer which both charges and discharges the print head capacitors.
[0098] In some examples, inductive energy transfer elements other than transformers are used to charge and discharge the print head capacitors. For example, a pair of two-terminal inductors could be used, or a single two-terminal inductor.
[0099] The drive voltage waveform described above includes a series of isolated trapezoidal pulses. However, in some examples, more complex pulse shapes such as a series of several closely-spaced varying-amplitude pulses, or pulses formed of a combination of stacked trapezoids (stepped pulses) are used.
[0100] It is to be understood that the foregoing description is intended to illustrate and not to limit the scope of the invention, which is defined by the scope of the appended claims. Other embodiments are within the scope of the following claims. | A method for regenerative driving of one or more transducers includes, for each of a plurality of driving cycles, enabling a number of transducers for driving, configuring a configurable capacitive energy storage element based on the number of enabled transducers and a desired overall capacitance, transferring a predetermined quantity of energy from a power supply to a first inductive energy transfer element, distributing the predetermined quantity of energy from the first inductive energy transfer element to the configurable capacitive energy storage element and to one or more other capacitive energy storage elements, each of the other capacitive energy storage elements coupled to an associated transducer, transferring energy from the one or more capacitive energy storage elements and from the configurable capacitive energy storage element to a second inductive energy transfer element, and transferring energy from the second inductive energy transfer element to the power supply. | 1 |
CROSS REFERENCE TO RELATED APPLICATIONS
[0001] This application is a continuation of U.S. patent application Ser. No. 10/337,484, filed Jan. 7, 2003, which is a continuation-in-part of U.S. patent application Ser. No. 09/558,706, filed Apr. 26, 2000, now U.S. Pat. No. 6,502,367, which is incorporated by reference as if fully set forth.
BACKGROUND
[0002] The present invention relates to the unloading of bulk bags used as containers for dry or moist particulate materials. The present invention more particularly relates to the unloading of bulk bag containers fabricated from cloth like material, such as woven polyester material, which is usually sewn in a cubical configuration.
[0003] Bulk bags made of heavy cloth material have been known in the art for sometime. It has also been known to provide the bag with heavy corner straps which support the bag when it is hung in a tower like support frame. The opposite end of the bag typically has a central outlet spout which is aligned with a discharge unit, for example a conveyer, hopper or the like, into which the material in the bag is intended to be discharged. Prior to discharge, the spout is maintained in a closed position, typically by tying-off of the spout.
[0004] To discharge the bag, the bag is hung in the support frame and the spout engaged with the discharge unit. The spout is opened and the particulate material flows via gravity through the spout. It is often desirable to control flow of material from the spout, for example, to permit batch weighing or to permit re-tying of the bag. Various types of bag closing devices, examples of which are illustrated in FIGS. 1-3 , have been employed. In the device of FIG. 1 , opposed bars, either flat or cylindrical, are moved together by fluid cylinders. As the spout is closed, it flattens in the direction of the arrows in FIG. 1 . As a result, the flattened, wide spout is difficult to re-tie, particularly if the spout is short. The device of FIG. 2 attempts to overcome such by providing substantially v-shaped opposed bars, as described in U.S. Pat. No. 5,787,689. However, at the two points of overlap between the opposed bars, the bag is susceptible to pinching which may cut the bag or the bag may roll out between the overlapped bars. Referring to FIG. 3 , a “claw” like device is shown. The bag is again susceptible to pinching in such a device. Additionally, in some applications, for example where the particulate material is dense, a significant amount of torque is required to closed the opposed claw members.
[0005] Accordingly, there is a need for an apparatus which assists in restricting a bag spout while reducing the likelihood of pinching of the spout.
[0006] It would also be desirable to provide a mechanical pinch valve for various other applications.
SUMMARY
[0007] The present invention provides a bag closing apparatus including a frame structure, a cinching assembly and an actuator assembly. The cinching assembly includes a plurality of pivot arms, each pivot arm including an arcuate portion and pivotably connected to the frame structure. The pivot arms are located relative to each other such that each pivot arm crosses at least one other pivot arms to define a confined closure area. The actuator assembly includes a plurality of actuators for moving the pivot arms between spread positions wherein the closure area has a predetermined area and closed positions wherein the closure area has a smaller area.
BRIEF DESCRIPTION OF THE DRAWINGS
[0008] FIGS. 1-3 are top plan views of prior art bag closing devices.
[0009] FIG. 4 is a top plan view of the preferred embodiment of the present invention.
[0010] FIG. 5 is a cross-sectional view of the housing of the preferred embodiment of the present invention.
[0011] FIG. 6 is an exploded view of the housing of the preferred embodiment of the present invention.
[0012] FIG. 7 is a top plan view of a pivot arm assembly of the preferred embodiment of the present invention.
[0013] FIG. 8 is a side elevation view of a portion of the pivot arm assembly along the line 8 - 8 in FIG. 7 .
[0014] FIG. 9 is a cross-sectional view along the line 9 - 9 in FIG. 4 .
[0015] FIG. 10 is a cross-sectional view along the line 10 - 10 in FIG. 4 .
[0016] FIG. 11 is a cross-sectional view along the line 11 - 11 in FIG. 4 .
[0017] FIGS. 12-14 are top plan views illustrating the cinching sequence of the cinching assembly of the preferred embodiment of the present invention.
[0018] FIG. 15 is a flow diagram of the preferred operating system of the present invention.
[0019] FIG. 16 is a top plan view illustrating the cinching assembly with the pivot arms extended to a position beyond the central region, shown in FIG. 14 , to an overlapped position.
[0020] FIG. 17 is a side profile view of the housing of a pinch valve in accordance with a second embodiment of the present invention excluding the cinching assembly.
[0021] FIG. 18 is a cross-sectional view along the line 18 - 18 in FIG. 17 .
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0022] The preferred embodiment of the present invention will be described with reference to the drawing figures where like numerals represent like elements throughout.
[0023] Referring to FIGS. 4-11 , the preferred embodiment 10 of the present invention is shown. The bag closing apparatus 10 comprises a housing 20 and a cinching assembly 60 . Referring to FIGS. 5 and 6 , the preferred housing 20 includes a split cylindrical body 30 secured between round top and bottom plates 24 and 40 . The plates have coaxial apertures 26 and 42 such that a cylindrical path 32 extends through the housing 20 . A plurality of mounting brackets 44 extend from the cylindrical body 30 for mounting the apparatus 10 on a frame (not shown) or other discharge unit (not shown). The body 30 , plates 24 , 40 and brackets 44 are preferably manufactured from sheet metal of approximately 10 or 12 gauge.
[0024] A pair of cylinder mounting boxes 34 are secured to the housing 20 in alignment with the open areas 31 of the split housing body 30 . Each box 34 has a mounting plate 36 with an aperture 38 extending therethrough. As will be described in more detail hereinafter, a fluid cylinder 81 is mounted to each mounting plate 36 with its piston rod 82 aligned with the respective aperture 38 . The boxes 34 are preferably manufactured from 14 gauge sheet metal and the plates 36 from one-quarter inch (3″) steel bar. The top and bottom plates 24 , 40 , the body 30 , the brackets 44 , the boxes 34 , and the mounting plates 36 are preferably welded together, but may be secured by other means.
[0025] A support ring 52 is preferably secured to the bottom plate 40 by a plurality of flanges 54 extending therefrom. The support ring 52 is preferably manufactured from a half inch (2″) steel rod and finished smooth on its upper surface. The support ring 52 provides support and a smooth guide surface for the pivot arms 72 as will be described in more detail hereinafter. A ring 28 depends from the top plate 24 about the aperture 26 . The ring 28 also provides a smooth guide surface for the pivot arms 72 as will be described in more detail hereinafter.
[0026] A removable support plate 48 with an aperture 50 therethrough may be attached to the top plate 24 with the apertures 50 and 26 coaxially aligned. The support plate aperture 50 is preferably sized to the dimension of the bag spout, i.e., if the spout has a sixteen inch (16″) diameter, the support plate aperture 50 will have a slightly oversized diameter. The support plate 48 thereby helps prevent sagging of the bag portion into the closing apparatus 10 . If a different size spout is used, the support plate 48 can be interchanged. An apertured guard 56 may be secured to the bottom plate 40 to help prevent unwanted objects from entering the apparatus 10 . The support plate 48 and the guard 56 are preferably manufactured from one-quarter inch (3″) high density polyethylene.
[0027] The cinching assembly 60 will be described with reference to FIGS. 7-11 . The preferred cinching assembly 60 comprises four pivot arm assemblies 70 and a pair of actuator assemblies 80 , although fewer or more of each may be utilized. Referring to FIGS. 7 and 8 , each pivot arm assembly 70 includes a substantially J-shaped pivot arm 72 extending from a pivot tube 76 . The pivot arms 72 are preferably manufactured from half inch (2″) steel rod and may be provided with a tapered tip. A link tab 74 extends from each pivot arm 72 for interconnection with a respective actuator assembly 80 . Each pivot tube 76 includes a hollow body 77 upon which a respective pivot arm 72 is mounted. A shaft 78 extends through the hollow body 77 and is pivotably secured with respect to the top and bottom plates 24 , 40 . Bushings 79 or the like may be utilized about the shaft 78 .
[0028] The preferred actuator assemblies 80 include fluid actuated cylinders 81 in communication with an air supply line or the like (not shown). A piston rod 82 extends from the cylinder 81 and is connected to an attachment plate 84 . A pair of link bars 88 , one above and one below, are pivotably connected to the attachment plate 84 via a pin 86 or the like. The opposite ends of the link bars 88 are then pivotably connected to a link tab 74 extending from a respective pivot arm 72 . By securing one link bar 88 above and one below the attachment plate 84 , the link bars 88 properly align with the link tabs 74 of the pivot arms 72 which are at different elevations. Alternatively, one actuator assembly 80 may be utilized for each pivot arm assembly 70 .
[0029] Referring to FIGS. 9-11 , the four pivot arms 72 a - 72 d are stacked one upon the other and upon the support ring 52 . The support ring 52 and top ring 28 are preferably spaced such that the pivot arms 72 a - 72 d abut, as shown in FIG. 10 , but remain slidable relative to one another. The abutting relationship helps prevent the spout from moving between adjacent pivot arms 72 . Referring to FIG. 11 , the pivot arms 72 a - 72 d are mounted at different heights on their respective pivot tubes 76 to provide proper alignment. Additionally, to provide proper alignment of the fluid actuated cylinders 81 , such are preferably mounted off-set from one another. As shown in FIG. 9 , the higher mounted cylinder 81 actuates pivot arms 72 a and 72 c and the lower mounted air cylinder 81 actuates pivot arms 72 b and 72 d.
[0030] The cinching sequence will now be described with reference to FIGS. 12-14 . Referring to FIG. 12 , the actuator assemblies 80 are non-energized and the pivot arms 72 are in an open, generally circular configuration. In this configuration, a spout can be passed through the assembly 10 and engaged with a discharge unit. When it is desired to close the spout, the fluid cylinders 81 are actuated to extend the rods 82 . The pivotably connected link bars 88 translate the linear force to move the pivotably connected pivot bars 72 along an arcuate path as represented by the arrows A in FIG. 13 . The arcuate path and the curvature of the pivot arms 72 minimizes the potential for pinching of the spout. Actuation of the cylinders 81 continues as the pivot arms 72 constrict the bag to a central region 90 . The pivot arms 72 are then extended to a position beyond the central region 90 , as shown in FIG. 16 , and overlap such that the bag spout forms a “Z” as it travels between the pivot arms 72 . The over extension is preferred, but may not be required in all applications.
[0031] The preferred operating system 100 of the closing assembly 10 will be described with reference to FIG. 15 . The preferred operating system 100 includes a manual valve 102 , a safety push button 104 , a selector switch 106 , a timer 108 , and an automatic control 110 . The manual valve 102 controls the flow of fluid into the cylinders 81 and is moveable between a neutral position and “close” and “open” positions wherein fluid is provided to the cylinders 81 to extend or retract the rods 82 . To operate the assembly 10 manually, an operator uses the manual valve 102 to control flow into and out of the cylinder 81 as desired. The system 100 also preferably includes a safety push button 104 which closes the fluid supply 101 unless engaged. If either the push button 104 or valve 102 is released, pressure to the cylinder 81 will cease. As such, the operator must use one hand to engage the push button 104 and the other to operate the manual valve 102 , thereby reducing the likelihood the operator will inadvertently place a hand in the path of the moving components.
[0032] In some instances, an operator may want to remove one or both hands while maintaining pressure in the cylinder 81 , for example, to retie the spout. As such, the preferred system 100 also includes an automatic control 110 . To utilize the automatic control 110 , the selector switch 106 must be in the “auto” position. If the switch 106 is in the “auto” position, the timer 108 will time the duration the manual valve 102 is in the “close” position. If the manual valve 102 is in the “close” position for a given time interval, for example five seconds, the timer 108 will trigger the automatic control 110 . The automatic control 110 will then continue to supply fluid pressure to the cylinder 81 , irrespective of whether the manual valve 102 or push button 104 are engaged, until the operator moves the selector switch 106 to a “manual” position. With the selector switch in the “manual” position, the operator can use the manual valve 102 to open the cinching assembly 60 . Other manual and automatic operating systems may also be used.
[0033] Referring to FIGS. 17 and 18 , a pinch valve 220 in accordance with a second embodiment of the present invention, for regulating material flow, is shown. The pinch valve 220 is adapted to be connected in a pipe 290 , and includes a housing with a first end 226 for receiving a material flow and a second end 242 for discharging the material flow. A cylindrical housing 230 contains an elastic bladder 201 through which the material flows. A mounting box 234 which is similar to the mounting box 34 discussed above, is secured to the cylindrical body 230 . Flanges 244 are attached to mating flanges on the conduit 290 to produce a closed material flow system. However, other types of connections could be used, including a threaded compression connection, a solder joint, and a weld joint.
[0034] The second embodiment of the pinch valve 220 employs a cinching assembly 60 and cinching sequence substantially identical to that of the described first embodiment. Actuators 281 attaches to mounting plate 236 as shown in FIG. 18 , which is in turn secured to mounting box 234 . A first plate 224 and a second plate 240 cooperate with shafts 277 , as shown in FIG. 17 , to form the cinching assembly 260 in the same manner as the cinching assembly 60 described above. When the actuators 281 are non-energized, the pivot arms 272 are in an open, generally circular configuration allowing full unhindered material flow through the bladder 201 . Actuating the fluid cylinders 281 causes rotation of the pivot arms 272 , in the same manner as the pivot arms 72 described above, thereby constricting the bladder and potentially reducing material flow. Material flow can be arrested completely when pivot arms 272 are extended to a closed position. Depending upon the material thickness of the bladder, the flow may be arrested without totally closing off the central region. | A bag closing apparatus including a frame structure, a cinching assembly and an actuator assembly. The cinching assembly includes at least three pivot arms, each pivot arm including an arcuate portion and pivotably connected to the frame structure. The pivot arms are located relative to each to define a confined closure area. The actuator assembly includes a plurality of actuators for moving the pivot arms between spread positions and closed positions wherein the closure area has a smaller area. | 5 |
FIELD OF THE INVENTION
The present invention relates to the use of cyclic adsorption processes for the removal of oxygen required for the purification of liquid argon. More specifically, the invention relates to the process steps, conditions, and adsorbents to purify a liquid argon stream of oxygen. The present invention also describes an optimal and economically attractive lower energy consumption process for obtaining a commercially viable liquid argon product. In addition, the invention also provides the identification of an optimal adsorbent for use in this purification process. This purification process can be integrated with an air separation plant or unit (ASU), under field service relevant conditions.
DESCRIPTION OF RELATED ART
Successful development of a cyclic adsorption process to achieve removal of low concentrations (i.e., in the range of parts per million) of oxygen from liquid argon, requires the identification of a suitable adsorbent as well as the development and optimization of the adsorption process steps.
The removal of low concentrations of oxygen from argon is considered to be a purification process and is necessary for many end users of argon where the presence of oxygen in the argon is undesirable. In many instances where safety, handling, and the industrial or laboratory use of argon in either a liquid or gaseous state occurs, the purity of argon is important. Argon is colorless, odorless, and nontoxic as a solid, liquid, and gas. Argon is chemically inert under most conditions. As an inert noble gas, it possesses special properties desirable for applications related to the semi-conductor industry, lighting, and other types of gas discharge tubes, welding and other high-temperature industrial processes where ordinarily non-reactive substances become reactive. Oxygen, in contrast to argon, is a highly reactive substance (in gaseous or liquid form) and is often a safety concern in that it supports combustion. Even low levels of oxygen (<100 parts per million) are many times not acceptable for certain laboratory and industrial processes. This also includes the chemical processing industry where certain reactions must be carried out primarily in the absence of oxygen. Cost considerations for the purification of argon have been a driving influence in the development of special cryogenic systems over at least several decades, and finding a suitable process which is robust, reliable, and meets the economic criteria necessary for customer demand has been sought. Production of liquid argon via cryogenic distillation is well known and is the preferred method of producing high purity argon.
Adsorption processes have also been described for the purification of argon, however, these have in general been limited to gas phase using 4A adsorbents and involved expensive energy intensive adsorption processes. For example, considerable cost is added to the adsorption process whenever an evacuation step is required. The adsorption process step of regeneration that requires vacuum has been historically very energy intensive in that vacuum processing requires special equipment and other additional peripherals leading to much higher energy demands as well as the addition of undesirable but necessary capital and operating expenses.
In the related art, U.S. Pat. No. 3,996,028 provides for purification of argon using an adsorption process to remove oxygen impurities by passing a contaminated argon stream through synthetic zeolites of the A type at cryogenic temperatures. The document provides for vacuum treatment as a necessary step for desorption of oxygen from the zeolite following a warm-up regeneration step. Moreover, during the adsorption step the argon feed is in the gaseous phase and, the purified argon product provided is in the gas phase.
U.S. Pat. No. 4,717,406 describes the on-site adsorption of impurities contained in liquefied gases by passing liquefied gases through an activated adsorbent material at cryogenic temperatures and pressures for a time sufficient to permit adsorption. However, a necessary component of this process includes filters upstream and downstream of the adsorbent bed. The examples that have been provided in this document pertain to the purification of liquified oxygen gas from carbon dioxide as this comes in contact with an adsorbent bed which is initially at ambient temperature.
U.S. Pat. No. 5,685,172 describes a process for the purification of oxygen and carbon dioxide from a cold gas or liquid stream of at least 90 mol % of nitrogen, helium, neon, argon, krypton, xenon, or a mixture of these gases. To achieve this, the use of a porous metal oxide, such as hopcalite-like materials are required. The regeneration of these metal oxides requires a reducing agent, such as hydrogen, which increases the total operating cost of adsorption processes using these materials. The zeolites described in the present invention are different than hopcalite and do not require use of reducing agents for regeneration. More specifically, hopcalites are chemisorbents or catalysts where zeolites, however, are reversible physical adsorbents. In addition, hopcalite materials are largely non-crystalline. Any crystallinity associated with hopcalite is attributed to the MnO 2 component which is present mainly in amorphous form. In contrast, zeolites are crystalline materials.
U.S. Pat. No. 6,083,301 describes a PSA or TSA process for purifying inert fluids to at most 1 part per billion impurities for use in the field of electronics. This patent describes the use of hopcalite-like adsorbent for the capture of oxygen impurities from liquid streams.
U.S. Pat. No. 5,784,898 also describes a cryogenic liquid purification process by which the liquid to be purified is brought in contact with an adsorbent to permit the adsorption of at least one of its contaminants. It is disclosed that at least a portion of the adsorbent is maintained cold using purified cryogenic liquid in between two subsequent purification cycles. Clearly, regeneration of the adsorbent is not described as a step that is provided in between the purification cycles. According to U.S. Pat. No. 5,784,898, following the completion of the purification cycle, the adsorbent is kept cold by coming into direct contact with a portion of the purified cryogenic liquid until the next purification cycle. Regeneration of the adsorbent takes place after a number of purification cycles and after draining the cryogenic liquid from the reactor.
In short, there are several limitations associated with the commercial purification of argon using adsorption techniques that have been discussed in the related art for certain applications. These known processes have been deficient in meeting all the criteria addressed above, namely: delivering argon as a liquid with very low oxygen concentration in an economic, lower energy consuming process. Another disadvantage is the required use of vacuum, which further increases energy demand, capital expenditures, and maintenance, and also further reduces the robust nature of any of the currently used or known argon purification processes. Further drawbacks include the fact the adsorbent systems which use commercially available zeolites of the 4A type require relatively large adsorbent beds to accomplish the purification necessary and these adsorbent beds must be taken “off-line” for frequent regeneration prior to restarting purification. Additional drawbacks associated with the related art also include the use of hopcalite-like adsorbents that do not possess the required physico-chemical properties needed for simple adsorbent regeneration and require the use of hydrogen as a reducing agent which is costly. These related art processes are not optimal for large scale operation in ASUs that produce up to a couple of hundred tons of liquid argon on a daily basis in that the TSA process of the present invention is a liquid compatible, continuous cyclic process, using a modified zeolite adsorbent.
Unmet needs remain regarding manufacture of large scale liquid argon purification with low parts per million levels (down to or below 1 part per million is desirable) of oxygen using adsorption technology. This includes the development of an optimal, economic, and effective adsorbent regeneration scheme as well as adsorbents with maximum capacity for oxygen uptake and negligible uptake for argon, which enables the use of smaller adsorbent beds.
To overcome the disadvantages of the related art, it is an object of the present invention to describe a novel process for liquid argon purification. This includes the use of a Temperature Swing Adsorption (TSA) process. The adsorbent is effectively regenerated by removing most of the adsorbed oxygen, by purging with a warm nitrogen and/or argon stream to above cryogenic temperatures.
It is also an object of the present invention to provide for a specific combination of a TSA process cycle along with the use of special forms of zeolite 4A material for providing the most efficient required separation. Some of the related art discloses the use of hopcalite materials to purify oxygen contaminants from liquid argon (see, e.g., U.S. Pat. Nos. 5,685,172 and 6,083,301). The use of 4A zeolite materials is also described in the cited art (e.g., U.S. Pat. No. 3,996,028), but in applications where the purification process takes place in the gas phase and requires a vacuum pretreatment step for the regeneration of the adsorbent. In the present invention, there is no need for a vacuum pretreatment step. The purification takes place in the liquid phase, and the adsorbent has been modified to accommodate the requirements of the new and unique process.
Other objects and aspects of the present disclosure will become apparent to one of ordinary skill in the art upon review of the specification, drawings, and claims appended hereto.
SUMMARY OF THE INVENTION
The present invention describes a TSA process for removing oxygen from liquid argon, comprising the following cyclical steps:
a) supplying the adsorbent bed with the liquid argon feed that contains oxygen, thereby producing a purified liquid argon product leaving the adsorbent bed with less oxygen than existing in the liquid argon feed;
b) draining the purified residual liquid argon product and removing this residual out of the bed and;
c) allowing the adsorbent bed holding the adsorbent to warm to a temperature such that the absorbent is regenerated to the point that the adsorbent bed can continue to remove the oxygen and continue to provide the purified liquid argon once the adsorbent bed is cooled down as described in step (d) below.
d) cooling an adsorbent bed holding adsorbent to a temperature such that the adsorbent bed sustains an argon feed in a liquid phase.
The process described above is a cycle operated in a fashion comprising steps (a)-(d) where the cycle is repeated, as needed, and the adsorbent bed contains zeolite adsorbents of either the 4A type zeolites or ion exchanged 4A type zeolites or both and where the ion exchange is accomplished with lithium ions. According to an aspect of the invention, a TSA cyclic process for the purification of liquid argon is provided in combination with the development and use of specific and special adsorbents. The adsorbents contained within the adsorbent beds are effectively regenerated to remove oxygen via desorption by warming the beds with various gases (e.g., nitrogen, argon or gas mixtures including purified air) at temperatures that may reach ambient conditions.
Also, the adsorption process for removing oxygen from liquid argon, may be further described as follows:
a) supplying from the inlet of an adsorbent bed the liquid argon feed that contains oxygen in the concentration range of about 10 to 10,000 parts per million, adsorbing at least part of the oxygen on the adsorbent thereby producing a purified liquid argon product leaving the adsorbent bed from the outlet with less than or equal to 1 parts per million of oxygen;
b) supplying a nitrogen purge at the outlet of the adsorbent bed and draining from the inlet of the adsorbent bed purified residual liquid argon and;
c) continuing the nitrogen purge at the outlet of the adsorbent bed and allowing the adsorbent bed containing the adsorbent to warm to a temperature of at least 200 degrees Kelvin, desorbing at least part of the adsorbed oxygen and removing this from the inlet of the adsorbent bed and;
d) supplying a gaseous argon purge of at least 200 degrees Kelvin at the outlet of the adsorbent bed, so that the gaseous effluent at the inlet side of the adsorbent bed is predominantly argon;
e) indirectly cooling the adsorbent bed containing adsorbent, where the bed has an inlet and an outlet, as well as a direct and an indirect cooling means to a temperature below about 150 degrees Kelvin and;
f) directly cooling the adsorbent bed with purified liquid argon to a temperature such that the adsorbent bed sustains an argon feed in a liquid phase, such that g) the process steps (a)-(f) are repeated in a cyclical manner.
The economic advantages provided by the current invention include the reduction of capital cost of more conventional alternative technologies aimed at purifying liquid argon from oxygen impurities by use of adsorption processes. This reduction in capital cost is a result of the combination of an economically attractive adsorption process cycle, especially as it pertains to the regeneration step (e.g., elimination of any vacuum regeneration step), and the use of a synthetic zeolite material that does not require expensive reducing agents (e.g., hydrogen) to be regenerated.
BRIEF DESCRIPTION OF THE DRAWINGS
The objectives and advantages of the invention will be better understood from the following detailed description of the preferred embodiments thereof in connection with the accompanying FIGURE wherein like numbers denote the same features throughout
The FIGURE illustrates the steps for a cyclic TSA process as provided in the exemplary embodiments of the present invention.
DETAILED DESCRIPTION OF THE INVENTION
The present invention relates to and describes a combination of an adsorption process cycle with specific adsorbents to efficiently purify a liquid argon stream into a stream that is primarily free from oxygen impurities, and methods of making and using the associated process and adsorbent bed.
More specifically, in the present invention, a TSA process has been developed, by which parts per million concentration levels of impurities of oxygen are removed from a liquid argon feed stream. The adsorbent for the TSA process has been selected and prepared so that the on-line time for each adsorbent bed is on the order of one week prior to any regeneration requirements. The purified liquid argon product should contain at most 10 parts per million of oxygen, and preferably less than or equal to 1 part per million of oxygen while the quantity of oxygen in the liquid feed is usually between 10 and 10,000 parts per million.
The bulk of the oxygen impurity adsorbed in the adsorbent is removed by increasing the temperature and using a suitable purge gas. The purge residual gas (e.g. argon, nitrogen, purified air) loading on the adsorbent, at the regeneration temperature, is substantially low such that the adsorbent, after cooling, is still able to remove significant amounts of oxygen from liquid argon streams in subsequent purification cycles.
The process includes several distinct process steps which are operated in sequence and repeated in a cyclical manner. Initially the impure (oxygen containing) cryogenic liquid argon is contacted with adsorbent during the purification or adsorption step, whereupon the oxygen impurities are substantially adsorbed by the adsorbent and a purified liquid argon product is obtained. Next, the oxygen contaminated liquid argon is drained from the adsorbent bed. After the draining of any residual cryogenic liquid is complete, the adsorbent bed is warmed to a predetermined temperature that allows for essentially complete regeneration of the adsorbent. Finally, cooling the regenerated adsorbent within the bed is provided in order that the purification process can begin again. These steps describe a single adsorption/purification cycle which is repeated as required.
Additionally, several key aspects of the cyclic adsorption/purification process are further described below. First, the process is preferably continuous and, therefore, the system requires at least two adsorbent beds; one of which carries-out the adsorption or purification step while another bed is being regenerated in preparation for a further adsorption or purification step. The choice of the number of beds required to keep the system operational and efficient is not limited and is dictated by system installation and process requirements and/or dictated by customer or application needs. It should be understood that the process described above often will include two or more adsorbent beds, wherein the process for purifying liquid argon in each bed is offset from one another. Specifically, for instance, when one adsorbent bed is being provided feed gas, a second adsorbent bed can be regenerating, a third adsorbent bed may be idle, and a fourth adsorbent bed may be cooling.
The purification step takes place at or below critical cryogenic temperatures to ensure the liquid state of argon feed persists at pressures in the range of 20-150 psig. However, purification at pressures higher than 150 psig, caused by a hydrostatic head pressure gain or pressurization of the feed using rotating equipment or a combination thereof, is an alternative way of practicing this invention. The oxygen level in the impure cryogenic liquid argon feed can range from as low as 10 parts per million to one or more thousand parts per million (preferably not more than 10,000 parts per million). The liquid argon feed is introduced at the bottom of the adsorbent bed. The purified liquid argon, collected at the top of the bed, is then subsequently sent to a holding product tank. The purification step is completed once the oxygen level in the liquid argon product reaches the desirable purification level of less than or equal to 10 parts per million and preferably less than or equal to 1 part per million of oxygen in argon.
Next, the bed is purged with an inert gas to drain the liquid contained in the adsorbent bed prior to regeneration. The inert purge gas can be either nitrogen, or argon or a mixture of both, or even purified air. The temperature of the inert gas is at least at the preferred gas boiling point and more preferably near ambient temperature, while its pressure is at least 2 psig and more preferably at least 15 psig. The draining step is completed once all the liquid that was contained in the adsorbent bed is drained.
Once the draining step is completed, the regeneration step is initiated. During this step, the temperature of the adsorbent bed increases as it is contacted with the purge gas until the bed temperature reaches at least 200 degrees Kelvin and more preferably around ambient temperature. The purge gas for the regeneration step is preferably either nitrogen or argon or a mixture of both. In cases where nitrogen and/or argon are less readily available other gases can be used to purge the adsorbent bed and regenerate the adsorbent including mixtures of dry carbon dioxide and hydrocarbon free air or a mixture of nitrogen and oxygen. Alternatively, the bed can be initially purged with nitrogen followed by an argon purge. The temperature of the purge gas is at least 120 degrees Kelvin and more preferably near ambient temperature, while the pressure is at least 2 psig and more preferably at least 15 psig. The temperature of the purge gas could be higher than ambient temperature, with the proviso that the porous adsorbent has enough thermal stability to withstand a higher temperature purge. In the most preferred embodiment, the purge gas is introduced from the top portion towards the bottom portion of the bed, in a direction counter current to the liquid feed stream. Purging the bed from the bottom portion to the top portion, in the same direction as the flow of the liquid to be purified are alternative embodiments which can accomplish similar results, with the proviso that the bed is below the fluidization limit or that the adsorbent and the bed is fully contained.
At the end of the regeneration step, the adsorbent bed reaches a temperature of at least 200 degrees Kelvin, and more preferably around ambient temperature. To proceed to the next purification cycle, the bed should be cooled to a temperature below the argon boiling point. One way to achieve this is via indirect cooling, i.e. by flowing liquid nitrogen (at a pressure ranging from about 18-30 psig) or cold gaseous nitrogen or liquid argon through a jacket surrounding the adsorbent vessel until the bed temperature, as measured at the center of the bed, has reached the preferred temperature. In one embodiment, this temperature is approximately 90 degrees Kelvin when the pressure of the liquid feed is about 60 psig. A most preferred way to achieve this is through a combination of two cooling steps. During the first step, indirect cooling is provided to the adsorbent bed, i.e. by flowing liquid nitrogen through a jacket surrounding the adsorbent vessel until the bed temperature, as measured at the center of the bed, has reached approximately 120 degrees Kelvin. Subsequently, during the second cooling step, the bed is cooled to approximately 90 degrees Kelvin by flowing liquid argon directly through the bed. This liquid argon stream could either be obtained from the impure liquid argon feed or from a portion of the purified liquid argon product, depending on the choice of design of the process. The subsequent purification step can be initiated once the bed has reached a temperature of 90 degrees Kelvin.
The development of a preferred cyclic cryogenic adsorption process depends to a high degree on the ability to warm and cool the absorbent bed within a specified and optimal time period. It will be understood by those skilled in the art that for a two-bed process, the time to drain the adsorbent bed and the heating (for adsorbent regeneration) and cooling time period also provides a key process variable and time frame for the “on-line time” of each absorbent bed. Furthermore, it is desirable from a process and economics standpoint to not cycle each bed very frequently. The preferable online time requirement for each bed is at least one week.
There are alternative process methodologies that could be used to practice the present inventive disclosure, however the most preferred embodiment is discussed below, with reference to the FIGURE.
For purposes of explanation and simplicity, the use of a single adsorbent bed is described and shown in the FIGURE. However, it will be understood by those skilled in the art, that the process described will be provided for two or more beds for the sake of the continuity of the process.
With reference to the exemplary embodiment of the FIGURE, the individual consecutive steps for a cyclic TSA process employed in the present invention are shown. In the initial stage of set-up, the absorbent bed ( 100 ) is tightly packed with adsorbent material ( 200 ). External cooling with liquid nitrogen is provided via a cooling jacket ( 300 ) that surrounds the bed. Stage (A) depicts the initial set-up arrangement prior to the beginning of purification, where the adsorbent bed is at about 90 degrees Kelvin. Stage (B) illustrates the purification step of the adsorption process. During Stage (B), the liquid argon stream containing oxygen is fed into the adsorbent bed as represented by the arrow ( 1 ). The feed is provided at the bottom of the bed. This feed stream ( 1 ) is liquid phase argon that contains oxygen impurities in the range of 10 to 10,000 parts per million of oxygen. The pressure within the bed during the introduction of the liquid argon feed is about 60 psig and the corresponding temperature for this exemplary embodiment ensured that the argon feed remained in the liquid phase at the respective process pressure conditions, namely a temperature of about 90 degrees Kelvin. The adsorbent is selected so that under the purification conditions, the absorbent is selective for oxygen. The liquid argon product stream ( 2 ) is collected at the top end of the bed. The purification step is completed once the level of oxygen in the liquid argon product reaches a concentration of 1 part per million. At this instance, the online bed should be prepared for regeneration and the second bed is brought online to perform the purification.
Prior to regeneration of the adsorbent, the liquid argon volume in the bed is drained as shown in Stage (C). In order to ensure that the bed is drained properly and in a timely fashion, a purge step is provided using an inert gas (normally either argon or nitrogen) denoted as stream ( 3 ). The temperature of the inert gas is about 300 degrees Kelvin, while its pressure is preferably about 15 psig. The draining step is completed once all the liquid that was contained in the adsorbent bed is drained. The liquid drain stream ( 4 ), as provided and shown, is rich in liquid argon that remained contaminated with oxygen and collected at the bottom of the bed. The liquid nitrogen was also drained from the cooling jacket and vented to the atmosphere.
After bed ( 100 ) is drained, the adsorbent is regenerated using a warm purge gas while the adsorbent remains within the same bed ( 100 ). As illustrated in Stages (D) and (E), a nitrogen purge through the bed was initiated in a countercurrent fashion in relation to the feed (i.e. from the top portion to the bottom portion of the bed). The temperature and pressure of the nitrogen purge gas, stream ( 5 ) and ( 7 ), is about 300 degrees Kelvin and 15 psig, respectively. The effluent during the purge Stage (D), indicated as stream ( 6 ), was predominantly composed of undesirable oxygen contaminant, and some argon in the nitrogen purge gas. During this step, oxygen is desorbed from the zeolite adsorbent and some quantity of argon is desorbed as the temperature within the absorbent bed rises. As the purging continues, and the bed temperature approaches the temperature of the purge gas (shown as nitrogen in stream ( 7 )), the gaseous effluent, stream ( 8 ), becomes predominantly nitrogen (Stage (E)). The nitrogen purge is completed when the bed temperature reaches about 300 degrees Kelvin. At that point, the zeolite becomes loaded with nitrogen. To obtain optimum performance for the liquid argon purification process of this invention, it was necessary to leave most of the available sites of the adsorbent free and capable of capturing a majority of oxygen impurities. Hence, subsequent to the nitrogen gas purge, an argon gas purge, indicated by the stream ( 9 ) shown, is implemented (Stage (F)). The temperature of the gaseous argon for purge is about 300 degrees Kelvin, while the pressure is around 15 psig. This is a very important step in the regeneration of the adsorption scheme. During the last part of the regeneration step, (Stage (F)), a gaseous effluent of nitrogen and argon exits the bed ( 100 ), indicated by stream ( 10 ). The argon gas purge is completed when the effluent, stream ( 10 ) is predominantly argon gas. At this instance, the argon gas occupies the macropore space of the adsorbent particles as well as the void space between particles within the adsorbent bed.
Cooling the adsorbent begins in Stage (G). During this stage, indirect heat transfer from a liquid nitrogen medium flowing in a jacket ( 300 ) surrounding the bed ( 100 ) cooled the adsorbent bed to approximately 120 degrees Kelvin. The pressure of the liquid nitrogen in the jacket is regulated so that the liquid nitrogen temperature is above the melting point of argon at the process conditions and below the saturation point of nitrogen. Once the temperature in the middle of the adsorbent bed is about 120 degrees Kelvin, the direct cooling step is initiated, as shown in Stage (H). This involves direct contact of the adsorbent material ( 200 ) with a purified liquid argon stream denoted stream ( 11 ). Stream ( 11 ) is introduced at the bottom of the adsorbent bed and it cools the bed to the desired temperature for purification of about 90 degrees Kelvin. This also facilitates building a liquid head to fill the adsorbent bed with purified liquid argon. At the end of this step the temperature at the middle of the bed is about 90 degrees Kelvin and the pressure is around 60 psig. This allows for the next purification cycle to begin again at Stage (A).
Hence, in the context of the current invention, a full TSA purification cycle involves the following steps:
(i) providing the adsorbent bed with either virgin or regenerated adsorbent—Stage (A)
(ii) purification of the liquid argon feed providing making purified liquid argon product—Stage (B)
(ii) drainage of the liquid argon contained in the bed at the end of purification step—Stage (C)
(iii) regeneration of the adsorbent via warm-up—Stages (D), (E), and (F) and;
(iv) cool-down of the adsorbent bed—Stages (G) and (H) so that the cycle can be repeated.
In describing the adsorbent, it is instructive to understand the need for the proper adsorbent which will adsorb, at most, very small amounts of argon. The ideal adsorbent does not adsorb any argon and also removes impurities from the argon which are predominantly oxygen impurities. However, in practice, the adsorbents that have been used still have some argon uptake capacity. Herein are described adsorbents specifically designed to minimize argon uptake.
The adsorbents that were developed for the present invention are primarily beads (with predominantly spherical particle geometry) with an average particle size of less than or equal to 2.0 mm and more preferably less than or equal to 1.0 mm. Additionally, the desired adsorbents have a porosity that is in a range of between 33 and 40 percent as measured by mercury (Hg) porosimetry. A binder is used to formulate the beaded absorbent, such that the binder is present at no greater than 15 weight percent. This binder is preferably purified versions of attapulgite, halloysite, sepiolite or mixtures thereof.
Testing to establish the viability of this purification cycle was performed in a pilot plant which included an adsorbent bed with a tube-in-tube type cooling system. The inner tube, which had an outside diameter of one inch, was packed with the adsorbent. The outer jacket was utilized for passive cooling. The length of the bed was either one foot or three feet. This bed allowed for receiving cryogenic liquid flow into an inlet section and the delivery of a cryogenic liquid product at the outlet. The bed was regenerated on-line as is described above.
Description of the Oxygen Breakthrough Test:
Experiments were performed on the pilot plant scale in order to understand several factors associated with the importance of the adsorbent particle size and binder type in affecting the performance of the liquid argon purification of oxygen impurities. These are characterized as “breakthrough-type” experiments. The general methodology of a breakthrough test is well-known to those skilled in the art. For the purpose of the present invention, the breakthrough or working capacity for oxygen (O 2 ) was determined using an overall mass balance of oxygen in the feed and in the effluent streams at a predetermined oxygen concentration at the outlet. For the purpose of the present invention, this concentration is 1 part per million unless otherwise specified. The dynamic working capacity (or dynamic capacity) of the oxygen adsorbate was established here to represent the ability of the adsorbent to remove oxygen contaminants to a certain level. The dynamic capacity of oxygen was determined from the oxygen breakthrough test and was used as an indicator of the ability of the adsorbent to remove oxygen from the feed stream. The conditions of the test were carefully selected to critically evaluate adsorbents for the desired adsorption capability under realistic process conditions.
The oxygen dynamic capacity was calculated based on Equation (1):
Δ
O
2
=
m
in
w
s
∫
0
t
b
(
y
in
-
y
out
)
ⅆ
t
(
1
)
Where:
m in is the molar feed flow into the bed
y in and y out are the inlet and outlet mole fractions of oxygen respectively
w s is the mass of adsorbent;
and;
t b is the breakthrough time corresponding to a predetermined breakthrough concentration (in this case—1 part per million oxygen unless otherwise specified).
The dynamic capacity inherently captures kinetic effects resulting from mass transfer resistance. For the purpose of this invention, the primary component in the liquid feed of the breakthrough test was argon. Because the concentration of argon in the feed stream was overwhelming in comparison to that of the oxygen concentration, the co-adsorption effect of oxygen upon argon was negligible. Conversely, the co-adsorption of argon might have had a significant effect upon the adsorption of oxygen. The breakthrough method, as described, was a preferred method for establishing the dynamic capacity for oxygen because argon co-adsorption and mass transfer effects were automatically incorporated into the resultant oxygen loading. Therefore, the preferred adsorbent is one that exhibits high oxygen dynamic capacity (long breakthrough times) in the presence of such inhibiting factors.
The following example is provided to demonstrate the capability of the TSA process, which demonstrates one embodiment of the present invention, i.e., to remove oxygen to concentrations of less than 1 part per million from a liquid argon stream that contains 10 parts per million of oxygen or more.
EXAMPLE 1
TSA Process Cycle Using Sample A
Preparation and Cool-down of Adsorbent Bed:
Sample A (266.58 g), a 42% lithium exchanged on an equivalent charge basis zeolite 4A, the development of which is described below (see Example 3), was loaded on a pilot plant bed. The length of the bed was three feet and the internal diameter of the bed was 0.88 inches. The bed was purged with gaseous nitrogen at 15 psig and 300 degrees Kelvin overnight. The nitrogen flow rate was 5 slpm. The gaseous nitrogen flow was discontinued and a gaseous argon purge was initiated at 15 psig and 300 degrees Kelvin with a gaseous argon purge time of no less than 20 min. The argon flow rate was 7.2 slpm.
Subsequent to the argon purge, the flow through the bed was discontinued and passive cooling of the bed was initiated by flowing liquid nitrogen into the jacket that surrounds the absorbent bed. The bed was cooled for at least 1 hour, or until the temperature as measured by a thermocouple in the middle of the bed, reached at least 120 degrees Kelvin. At this instant, purified liquid argon at 20 slpm was introduced from the bottom portion of the bed towards the top portion of the bed for at least a 45 minute period or until the bed temperature, as measured by the thermocouple reached 90 degrees Kelvin.
First Purification/Breakthrough Step:
When the bed temperature reached 90 degrees Kelvin, the liquid argon flow was discontinued and the introduction of a liquid argon stream with 99 parts per million of oxygen contaminant was initiated. The flow rate continued at 20 slpm.
The introduction of the contaminated liquid argon feed (with 99 parts per million of oxygen) into the adsorbent bed marked the beginning of the purification step (Stage (B) in the FIGURE). The flow direction of the liquid argon feed stream was from the bottom portion towards the top portion of the bed. After 17.1 hours, the oxygen concentration at the outlet of the bed reached 1 part per million. The dynamic capacity for this material for oxygen was calculated to be 1.13 weight percent corresponding to the breakthrough concentration of oxygen of 1 part per million. After 17.1 hours, the adsorbent and bed was ready for regeneration.
Drainage Step:
Following the end of the purification/breakthrough step above, the remaining liquid argon was pushed out of the bed by flowing nitrogen at 5 slpm (Stage (C) in the FIGURE). At the same time, gaseous nitrogen was allowed to flow in the jacket around the absorbent bed to initiate evaporation of the liquid nitrogen and transition to the following step, which is the warm regeneration.
Regeneration Step:
Following the completion of the drainage step, the regeneration step was initiated (Stage (D) in the FIGURE). The nitrogen purge was continued overnight and the pressure and temperature of the purge stream was kept at 15 psig and 300 degrees Kelvin respectively. After the gaseous nitrogen flow was discontinued, a gaseous argon purge was initiated at 15 psig and 300 degrees Kelvin with a gaseous argon purge time of no less than 20 minutes (Stage (F) in the FIGURE). The argon flow rate was 7.2 slpm.
Cool-down Step:
Subsequent to the argon purge, the flow through the bed was discontinued and passive cooling of the bed was initiated by flowing liquid nitrogen into the jacket that surrounds the absorbent bed (Stage (G) in the FIGURE). The bed was cooled for at least 1 hour, or until the temperature as measured by a thermocouple in the middle of the bed, reached 120 degrees Kelvin. At this instant, purified liquid argon at 20 slpm was introduced from the bottom portion of the bed towards the top portion of the bed for at least a 45 minute period or until the bed temperature, as measured by the thermocouple, reached 90 degrees Kelvin.
Second Purification/Breakthrough Step:
The adsorbent bed was now fully prepared for proceeding with the subsequent purification step. The concentration of oxygen in the liquid argon feed was kept at 100 parts per million. The concentration of the oxygen at the bed outlet was 1 part per million after 17.5 hours following introduction of the liquid feed into the bed. In this case, the dynamic capacity for oxygen was determined to be 1.21 weight percent at a breakthrough concentration of oxygen of 1 part per million.
In comparing the results from the first and second purification steps, it is clear that the regeneration step of the TSA process accomplished the goal of reducing and maintaining the oxygen level of the liquid argon product to below 1 part per million of oxygen over essentially the same period of time. Hence, the same purification performance was achieved in two consecutive cycles. This indicates that the ability of the adsorbent to remove oxygen from an oxygen contaminated liquid argon feed is fully restored after the described regeneration scheme is completed. After the regeneration step, the adsorbent still exhibits nearly the same oxygen capacity, thus confirming that the combination of the proper adsorbent with the proper process steps provides the desired resultant product using the process in a reproducible manner.
TABLE 1
Summary of Process Performance Data*
Initial
Final
O 2 Dynamic
Purification
Concen-
Concen-
Capacity
Step Before
tration
tration
Purifi-
measured at
and After
of Oxygen
of Oxygen
cation
1 part per
Adsorbent
Impurity
Impurity
Step Time
million
Regeneration
(ppm)
(ppm)
(hr)
(wt %)
1st
99
1
17.1
1.13
Purification
2 nd
100
1
17.5
1.21
Purification
After
Regeneration
*The average particle diameter of the adsorbent was 1.0 mm and the process used is as described and shown in the Figure
As shown by the data summarized in Table 1 above, the present disclosure and accompanying invention combines an advantageous adsorption process cycle with the adsorbent that has proper oxygen capacity and selectivity to efficiently purify a liquid argon stream contaminated with oxygen so that the oxygen levels are reduced and minimized to levels below 1 part per million. The cyclic TSA process is robust in that the oxygen dynamic capacity of the adsorbent remains essentially the same after subsequent regeneration of the adsorbent. The cyclic purification process is amenable with use of any adsorbent possessing the characteristics required to achieve the purification of the argon by removing oxygen.
The following example describes a TSA process for the purification of liquid argon from oxygen that is different than that described in Example 1 in that the regeneration step includes a warm nitrogen purge only, as opposed to a nitrogen purge followed by an argon purge (as described in Example 1).
EXAMPLE 2
Alternative TSA Process Cycle Using Sample A
Preparation and Cool-down of Adsorbent Bed:
The preparation and cool-down of the adsorbent bed was identical to that provided for Example 1, above. Sample A (92.24 g) was loaded on the pilot plant bed. The length of the bed for this example was one foot and the internal diameter of the bed was 0.88 inches. The bed was purged with gaseous nitrogen and argon as described in Example 1.
Subsequent to the argon purge, the flow through the bed was discontinued and passive cooling of the bed was initiated as described in Example 1. Following the passive cooling step, purified liquid argon at 40 slpm was introduced from the bottom portion of the bed towards the top portion of the bed for at least a 45 minute period or until the bed temperature, as measured by the thermocouple, reached 90 degrees Kelvin.
First Purification/Breakthrough Step:
When the bed temperature reached 90 degrees Kelvin, the liquid argon flow was discontinued and the introduction of a liquid argon stream with 1022 parts per million of oxygen contaminant was initiated. The flow rate continued at 40 slpm. The flow direction of the liquid argon feed stream was as described in Example 1. For Example 2, the capacity of the adsorbent bed at full breakthrough was calculated. This calculation was performed using Equation (1), above, where t b is now the time that corresponds to the full breakthrough, meaning the time when the oxygen concentration at the outlet of the bed reaches the inlet feed oxygen concentration (1022 parts per million, for the present example). Full breakthrough was achieved after 20.1 hours. The full bed capacity for oxygen was thus calculated to be 16 weight percent. Following the full breakthrough, the adsorbent and bed was ready for regeneration.
Drainage Step:
The adsorbent bed was drained from the remaining liquid argon as described in Example 1.
Regeneration Step:
Following the completion of the drainage step, the regeneration step was initiated (Stage (D) in the FIGURE). The nitrogen purge at a flow rate of 5 slpm was continued over a whole weekend and the pressure and temperature of the purge stream was kept at 15 psig and 300 degrees Kelvin respectively.
Cool-down Step:
Subsequent to the nitrogen purge, the flow through the bed was discontinued and passive cooling of the bed was initiated as described in Example 1. After the passive cooling step was completed, purified liquid argon at 40 slpm was introduced from the bottom portion of the bed towards the top portion of the bed for at least a 45 minute period or until the bed temperature, as measured by the thermocouple, reached 90 degrees Kelvin.
Second Purification/Breakthrough Step:
The adsorbent bed was now fully prepared for proceeding with the subsequent purification/breakthrough step. The concentration of oxygen in the liquid argon feed was kept at 997 parts per million. The concentration of the oxygen at the bed outlet 20 hours after the introduction of the liquid feed into the bed was that of the inlet (approximately 997 parts per million). The full bed capacity for oxygen was calculated to be 10.2 weight percent under the conditions described.
In comparing the results from the first and second full breakthrough steps, it is clear that the regeneration step of the TSA process did not accomplish the goal of restoring the initial adsorbent bed capacity for oxygen. The results reported showed a 36 percent decrease in the capacity of the adsorbent for oxygen following the regeneration method described in this example. This indicates that the regeneration scheme which involves a warm nitrogen purge only (as described in Example 2) is inferior and insufficient compared to the regeneration step which combines a warm nitrogen purge followed by a warm argon purge (as described in Example 1). Use of only the warm nitrogen purge does not fully restore the adsorbent bed capacity to remove the oxygen impurities in the subsequent purification step.
EXAMPLE 3
Preparation of Sample A (42% Lithium Exchange of Commercial 1.0 mm 4A+12% Actigel®)
A commercially produced zeolite 4A sample with 12% Actigel® in beaded form, having an average particle size of 1.0 mm was obtained from Zeochem LLC of Louisville, Ky.
On a dry weight basis, 450 g of the commercially produced sample (562 g wet weight) was stirred in a lithium chloride (LiCl) solution (60.71 g LiCl crystals dissolved in 1500 ml deionized water) for 2 hours at a temperature of 90 degrees Centigrade. This exchange was repeated two more times. After the first two exchanges, the beads were decanted and washed by stirring in 2000 ml deionized water for 15 minutes at 90 degrees Centigrade. Decant and wash steps were repeated two more times. For the final washing step after the third exchange, the beads were placed in a 1.0 inch diameter glass column and using a peristaltic pump, 20 Liters deionized water were pumped through the column at rate of 80 ml/minute at 80 degrees Centigrade. The beads were removed, air dried, screened to the 16×20 mesh size, then activated using a shallow tray calcination method using a General Signal Company Blue M Electric oven equipped with a dry air purge. The adsorbents were spread out in stainless steel mesh trays to provide a thin layer less than 0.5 inch deep. A purge of 200 SCFH of dry air was fed to the oven during calcination. The temperature was set to 90 degrees Centigrade followed by a 360 minute dwell time. The temperature was then increased to 200 degrees Centigrade gradually over the course of a 360 minute period (approximate ramp rate=0.31 degrees Centigrade/minute), and then further increased to 300 degrees Centigrade over a 120 minute period (approximate ramp rate=0.83 degrees Centigrade/minute) and finally increased to 593 degrees Centigrade over a 180 minute period (approximate ramp rate=1.63 degrees Centigrade/minute) and held there for 45 minutes. The 1.0 mm (16×20 mesh) product was characterized by Hg porosimetry to assess porosity characteristics. Chemical analysis of the Li exchange product using standard ICP (Inductively Coupled Plasma Spectroscopy) methods known by those skilled in the art yielded a lithium exchange level of 42% for this sample on a charge equivalent basis.
The following examples provide additional information with regard to experimental evidence which eventually led to the present invention. The advantage of the adsorbents developed and employed versus those commercially available and described in the related art is also further developed herewithin.
EXAMPLE 4
Samples B and C (Commercial 2.0 Mm and 1.7 Mm Zeolite 4A)
Samples B and C were obtained from a commercial manufacturer. The zeolite is known as Zeochem Z4-04 and manufactured by Zeochem L.L.C of Louisville, Ky. They were manufactured using greater than 12 weight percent of a clay, non-Actigel® type binder. The average particle diameter of Samples B and C was 2.0 mm and 1.7 mm respectively.
EXAMPLE 5
Preparation of Sample D (Laboratory 0.6 Mm Zeolite 4A from 3A Powder+12% Actigel®—Nauta Mixing)
Samples D was a zeolite 4A laboratory sample that contained 12 weight percent of Actigel®, a purified clay binder. This sample was prepared through ion exchange of a zeolite 3A product as described below.
On a dry weight basis, 2100.0 g of zeolite 3A powder (2592.6 g wet weight) was mixed with 286.4 g Actigel 208 (364.9 g wet weight) and 63.0 g F4M Methocel in a Hobart mixer for 1 hour and 35 minutes. The intermediate mixed powder from the Hobart mixer was transferred to a Nauta mixer having an internal volume of ˜1 ft 3 and agitated therein at a speed of 9 rpm. Mixing with the Nauta device was continued, while gradually adding de-ionized water to form beads having porosity in the range 30 to 35 percent, as measured after calcination using a Micromeritics Autopore IV Hg porosimeter. At the end of this mixing period, beads in the target size 0.6 mm (20×40 mesh) were formed. The product beads were air dried overnight prior to calcination using the shallow tray method at temperatures up to 593 degrees Centigrade. The shallow tray calcination method described in Example 3 was used. The calcined beads were subjected to a screening operation to determine the yield. The particles in the 20×40 mesh size range were harvested for further processing, including the steps of hydration, sodium (Na) ion exchange, and activation up to 593 degrees Centigrade under dry air purge.
Sodium exchange of the samples (to a sodium exchange level of at least 99 percent sodium on an charge equivalent basis) was achieved using the following procedure: A column ion exchange process was used where the samples are packed inside a glass column (dimensions: 3-inch i.d.) contacted with sodium chloride solution (1.0 M) at 90 degrees Centigrade at a de-ionized water flow rate of 15 ml/min. A preheating zone before the adsorbent packed column ensured that the solution temperature had reached the target value prior to contacting the zeolite samples. A 5-fold excess of solution was contacted with the samples to yield products with sodium contents of at least 99 percent exchange and above. After the required amount of solution was pumped through the column containing the samples, the feed was switched to de-ionized water to remove excess sodium chloride (NaCl) from the samples. A de-ionized water volume of 50 L and flow rate of 80 ml/min was used. A silver nitrate (AgNO 3 ) test, familiar to those skilled in the art, was used to verify that the effluent was essentially chloride free, at the end of the washing stage. The wet samples were then dried, rescreened to 0.6 mm (Sample D), and activated under dry air purge (flow rate 200 SCFH) using the shallow tray calcination method described above.
EXAMPLE 6
Preparation of Samples E and F (Laboratory 1.0 mm and 0.6 mm Zeolite 4A from 4A Powder+12% % Actigel®—Nauta Mixing)
Samples E and F were zeolite 4A laboratory samples that also contained 12 weight percent of the Actigel® binder, however these were prepared directly from a zeolite 4A powder. The samples were prepared using a Nauta mixer as described below.
On a dry weight basis, 2100.0 g of zeolite 4A powder (2592.6 g wet weight) was mixed with 286.4 g Actigel 208 (364.9 g wet weight) and 63.0 g F4M Methocel in a Hobart mixer for 1 hour and 35 minutes. The intermediate mixed powder from the Hobart mixer was transferred to a Nauta mixer having an internal volume of ˜1 ft 3 and agitated therein at a speed of 9 rpm. Mixing using the Nauta device was continued, while gradually adding de-ionized water to form beads having porosity in the range 30 to 35 percent, as measured after calcination using a Micromeritics Autopore IV Hg porosimeter. At the end of this mixing period, beads, including those in the target 16×20 and 20×40 mesh size range had formed. The product beads were air dried overnight prior to calcination using the shallow tray method at temperatures up to 593 degrees Centigrade, as described in Example 3. The calcined beads were subjected to a screening operation to determine the yield. The particles that were harvested were 1.0 mm in size (16×20 mesh) for Sample E, and 0.6 mm in size (20×40 mesh) for Sample F. Next, the beads were activated under dry air purge (flow rate 200 SCFH) using the shallow tray calcination method as described above in Example 3.
Characterization of Samples of Different Size Using an Oxygen Breakthrough Test
Tests were conducted with different sized zeolite 4A samples to determine oxygen breakthrough under identical process conditions as described above. For the test data provided in Table 2, the system pressure was 60 psig and the temperature during the purification process was controlled at 90 degrees Kelvin. The feed flow rate was 90 standard liters per minute (slpm) and the bed length was three feet. The feed concentration into the adsorbent bed was targeted to be either 1000 or 100 parts per million of oxygen (contaminant) in the liquid argon stream as specified in Table 2. This target was not achieved in all cases due to insufficient experimental control.
TABLE 2
Oxygen Breakthrough Performance Data
Inlet O 2
Purification Duration
Concen-
Time to Obtain
Adsorbent
tration
Outlet O 2
Outlet Concentration
Adsorbent
Average
in Liquid
Concen-
of O 2 at Less than
Sample
Diameter
Argon Feed
tration
1 part per million
Type
(mm)
(ppm)
(ppm)
(minutes)
Sample B 1
2.0
925
722
Not achieved
Sample C 1
1.7
910
403
Not achieved
Sample D 2
0.6
983
0.17
20
Sample C 1
1.7
90
31
Not achieved
Sample E 2
1.0
100
.03
43
Sample F 2
0.6
100
.02
131
1 = Commercially available adsorbent
2 = Laboratory prepared adsorbent
Table 2 shows that as the size of the absorbent material was reduced from 2.0 mm to 1.7 mm and then to 0.6 mm, the exit concentration of oxygen was reduced from 722 parts per million to 403 parts per million and then to 0.17 parts per million respectively, while the initial feed concentration was approximately 1,000 parts per million oxygen in liquid argon.
When the particle size of zeolite 4A was reduced to 0.6 mm (Sample D), the exit concentration of oxygen was 170 parts per billion and the bed allowed for purification of the liquid argon feed to below 1 part per million for a full 20 minute duration. Therefore, under the process conditions provided above, unless the zeolite 4A particle size is reduced to 0.6 mm, purifying liquid argon to less than 1 part per million oxygen, is not possible. These results indicate that the process of oxygen removal from a liquid argon stream is limited by the size of the absorbent material.
The same conclusion regarding the need to limit the size of the adsorbent can be reached when the feed concentration was initially set to approximately 100 parts per million of oxygen in liquid argon. Under these conditions, when the 1.7 mm zeolite 4A (Sample C) was used in the adsorbent bed, the outlet concentration of oxygen in liquid argon was reduced to 31 parts per million. When the 1.0 mm zeolite 4A (Sample E) was provided in the bed, purification of the liquid feed was achieved for a 43 minute duration. Finally, when the particle size of the 4A zeolite was reduced even more, to 0.6 mm (Sample F), the purification was extended to a 131 minute duration.
EXAMPLE 7
Preparation of Sample G (Laboratory 1.0 mm 4A Sample+12% Actigel®—Tilted Rotating Drum Mixing)
Sample G was another laboratory sample developed from zeolite 4A that also contained 12 weight percent of Actigel®. This sample was prepared using a tilted rotating drum mixer as described below.
On a dry weight basis, 9000.0 g of zeolite 4A powder (11029 g wet weight) was mixed with 1227.3 g Actigel 208 (1575.7 g wet weight) in a Simpson mixer-muller for 1 hour and 20 minutes. The mixed powdered intermediate mixed powder was transferred to a tilted rotating drum mixer having internal working volume of ˜75 L and agitated therein at a speed of 24 rpm. Mixing of the formulation was continued while adding de-ionized water gradually to form beads. A recycling operation was performed, involving grinding-up and reforming the beads until the beads exhibited a porosity, as measured by using a Micromeritics Autopore IV Hg porosimeter on the calcined product, in the range of 30 to 35 percent. At the end of this mixing time period, beads including those in the target 1.0 mm size (16×20 mesh) range were formed. The product beads were air dried overnight prior to calcination using the shallow tray method at temperatures up to 593 degrees Centigrade, as earlier described in Example 3. The calcined beads were subjected to a screening operation to both determine the yield and so that those particles could be harvested in the 16×20 mesh size range. Finally, the adsorbent particles were activated under dry air purge (flow rate 200 SCFH) again using the shallow tray calcination method as earlier described in Example 3.
EXAMPLE 8
Preparation of Sample H (Commercial 1.0 mm 4A+15-20% Non-Actigel® Type Binders)
Sample H was obtained from a commercial manufacturer. This was the zeolite 4A known as Zeochem Z4-01 and manufactured by Zeochem L.L.C. of Louisville, Ky. It is manufactured using traditional clay non-Actigel® type binders at a content of 15 to 20 weight percent.
Effect of Binder Type and Content in Oxygen Capacity of Zeolite 4A
Table 3 provides additional oxygen breakthrough data. Here the laboratory prepared zeolite 4A with 12 weight percent Actigel clay binder of Example 7 (Sample G) is compared to a commercial zeolite 4A of Example 8 (Sample H). The flowrate of the pilot plant during the purification step was 20 slpm for these breakthrough tests. Both of the beaded adsorbent products, (Samples G and H), were 1.0 mm in diameter. The breakthrough tests were carried out at a temperature of 90 degrees Kelvin, and a pressure of 68 psig. The liquid argon feed originally contained 100 parts per million of oxygen.
TABLE 3
Pilot Plant Performance Data*
Breakthrough
O 2 Dynamic
Binder % wt
Time to 1 part
Capacity at
Adsorbent
(Dry Weight
per million
1 part per
Type
Binder Type
Basis)
O 2 (min)
million (% wt)
Sample H 1
Mixture of
15-20
267
0.33
attapulgite,
kaolin,
bentonite
Sample G 2
Actigel
12
1022
1.17
*The average particle diameter of all adsorbents was 1.0 mm.
1 = Commercially available adsorbent
2 = Laboratory prepared adsorbent
The importance of the binder type and content for the present process is confirmed by the above performance data shown in Table 3. The comparison clearly shows that the oxygen dynamic capacity of Sample G is 3.5× greater than that of Sample H and therefore provides improved process purification performance. Since the binder content of Sample G is approximately 6% less than that of Sample H, one would expect an improvement in the equilibrium adsorption capacity. However, the 3.5× improvement in the dynamic capacity shown for Sample G would not be predicted simply by the difference in binder content between the two materials.
EXAMPLE 9
Preparation of Sample I (42% Lithium Exchange of Laboratory 4A+12% Actigel®—Tilted Rotating Drum Mixing)
Sample I was prepared in a similar fashion to that of Example 7 (Sample G) and then, it was partially ion exchanged with lithium using the following procedure.
On a dry weight basis, 12.53 lbs. of zeolite 4A powder (16.06 lbs. wet weight) was mixed with 1.71 lbs. of Actigel 208 (2.14 lbs. wet weight) in a Littleford LS-150 plow mixer for 10 minutes. The plow mixed powdered intermediate powder mixture was transferred to a tilted rotating drum mixer having internal working volume of ˜75 L and agitated therein at a speed of 24 rpm. Mixing of the formulation was continued while adding de-ionized water gradually to form beads. A recycling operation was performed, involving grinding-up and reforming the beads until the beads exhibited a porosity, which was measured using a Micromeritics Autopore IV Hg porosimeter on the calcined product, in the range of 30 to 35 percent. At the end of this mixing time period, beads—including those in the target 16×20 mesh size range, were formed. The product beads were then air dried overnight prior to calcination using the shallow tray method at temperatures up to 593 degrees Centigrade, as previously described in Example 3. The calcined beads were subjected to a screening operation, both to determine yield and also to harvest those particles that fell within the 16×20 mesh size range. The adsorbent particles were activated under dry air purge (flow rate 200 SCFH) using the same shallow tray calcination methods previously described.
Lithium ion exchange of the samples (to a Li ion exchange level of 42 percent on a charge equivalent basis) was achieved using the following procedure; a batch ion exchange process was used where 450 g of the sample on a dry weight basis was placed inside a glass beaker and stirred in a 1.5 L lithium chloride solution (0.95 M) at 90 degrees Centigrade for 2 hours. This was followed by stirring the sample in 2 Liters of de-ionized water at 90 degrees Centigrade for 15 minutes to remove excess lithium chloride. The exchange and wash process was repeated twice. Finally, the sample was packed in a glass column and washed with de-ionized water, similar to the procedure described in Example 3, to fully remove any excess lithium chloride. The wet samples were dried, rescreened to 16×20 sized mesh, and activated under dry air purge (flow rate 200 SCFH) again using the shallow tray calcination method described in Example 3.
Effect of Lithium Ion Exchange of Zeolite 4A in Process Performance
Evidence from testing indicates that argon also adsorbs in the micropores of zeolite 4A, but not as easily, and at a much lower observed rate than that of oxygen. The first experimental indication was obtained from single component McBain test data which showed a continuous increase in the argon uptake at 87 degrees Kelvin over 480 minutes during the adsorption test. Copending application entitled “Adsorbent Composition for Argon Purification” co-filed on Mar. 1, 2013 as Dckt. No. 13235 and incorporated herein by reference in its entirety, further describes the composition of the adsorbent(s) used in this process.
Breakthrough experiments under process relevant conditions have shown that the oxygen capacity of the 4A zeolite decreased by pre-exposing the freshly regenerated and indirectly cooled adsorbent to liquid argon. One purpose of these experiments was to simulate the conditions expected to occur for an industrial process utilizing a much longer adsorbent bed (e.g. 20 feet or more) rather than the prototype bed used in the pilot. When a much longer bed is utilized for the purification process, one skilled in the art understands that the portion of the bed close to the bed outlet is contacted with almost purified liquid argon for a long period of time (equal to the purification step time). Therefore, even if argon enters the micropores of the adsorbent at a much slower rate than oxygen, there is enough time at long cycle times, which are preferable for the current invention, for argon to adsorb at portions of the adsorbent bed close to the outlet. This argon adsorption on the adsorbent bed will in turn sacrifice the bed performance for oxygen adsorption. Hence, an adsorbent with minimum argon uptake is preferable. The experiments presented on Table 4 were performed in the pilot plant described above using a three foot long adsorbent bed. The process pressure and temperature during the purification stage of all tests were 67 psig and 90 degrees Kelvin, respectively. The feed flow rate was 20 slpm and the oxygen concentration in the argon stream was initially 100 parts per million.
TABLE 4
Pilot Plant Performance Data*
Percentage
Pre-exposure time
O 2 Dynamic Capacity
Lithium Ion
to liquid
at 1 part per
Adsorbent
Exchange
Ar (hr)
million (wt %)
Sample G 2
0
1.0
1.07
Sample G 2
0
48
0.35
Sample I 2
42
1.0
2.5
Sample I 2
42
48
2.0
*The average particle diameter of all adsorbents was 1.0 mm.
2 = Laboratory prepared adsorbent
Table 4 shows that, under these process conditions, the laboratory zeolite 4A sample (Sample G) lost 67 percent of its oxygen dynamic capacity after 48 hours of exposure to liquid argon prior to the oxygen breakthrough test. However, the 42 percent lithium exchanged laboratory zeolite A (Sample I) lost only 20 percent of its dynamic oxygen capacity after 48 hours of exposure to liquid argon prior to oxygen breakthrough testing. Therefore, the oxygen capacity is decreased to a much lesser extent following pre-exposure of a freshly regenerated and indirectly cooled 42 percent lithium exchanged 4A adsorbent to liquid argon than using a 4A adsorbent. If the adsorbent is not lithium ion exchanged, the adsorbent bed must be increased in size or a more frequent regeneration will be required to achieve the same argon purity results with the same process constraints. In addition, it has been determined that when the zeolite 4A is ion exchanged with 42 percent lithium on a charge equivalent basis (as for Sample I), the resulting material exhibits an increase in oxygen capacity.
Various modifications and changes may be made with respect to the foregoing detailed description and certain embodiments of the invention will become apparent to those skilled in the art, without departing from the spirit of the present disclosure. | The invention relates to a process for removing oxygen from liquid argon using a TSA (temperature swing adsorption) cyclical process that includes cooling an adsorbent bed to sustain argon in a liquid phase; supplying the adsorbent bed with a liquid argon feed that is contaminated with oxygen and purifying the liquid argon thereby producing an argon product with less oxygen contaminant than is in the initial liquid argon feed; draining the purified residual liquid argon product and sending purified argon out of the adsorbent bed. Regeneration of specially prepared adsorbent allows the adsorbent bed to warm up to temperatures that preclude the use of requiring either vacuum or evacuation of adsorbent from the bed. | 5 |
REFERENCE TO PRIOR APPLICATION
This application claims the benefit of U.S. Provisional Application No. 60/314,689, filed Aug. 24, 2001.
TECHNICAL FIELD
This invention relates in general to the field of gravel packing and stimulation systems for mineral production wells, and more particularly, to an improved method and system for performing gravel packing and stimulation operations.
BACKGROUND
In an effort to extract natural resources such as oil and gas, it is becoming increasingly common to drill a vertical well, and to subsequently branch off that well and continue to drill horizontally for hundreds or even thousands of feet. The common method for drilling horizontally will be described more fully below, but generally includes the steps of forming a fluid impermeable filter cake surrounding the natural well bore while drilling at the production zone, removing drilling fluid from the downhole service tools (washdown), performing gravel packing operations, and then removing the downhole service tools from the well bore. A stimulation tool is then run back into the well, and the well stimulated with the appropriate chemicals to remove the filter cake so that production may begin. The above-described method requires two “trips” down into the well bore with different tools to accomplish gravel packing and well stimulation. Each trip into the well can take as much as a day, with the cost of a rig running anywhere from $50,000.00 to $250,000.00 per day. Accordingly, achieving both gravel packing and stimulation in a single trip can be substantially beneficial. Further, each additional trip into the well also increases the risk of fluid loss from the formation. Fluid loss in some cases may substantially reduce the ability of the well to effectively produce hydrocarbons. Therefore, there is a need for a system and method that simply and reliably performs gravel packing and stimulation operations in a single trip into the well.
SUMMARY
In accordance with the present disclosure, there is a system which enable gravel packing and stimulating a horizontal well on a single trip into the well. Where a horizontal well is packed with a filter cake during a drilling operation, the present invention is used to gravel pack proximate to the production zone and stimulate the production zone by removing the filter cake, all in a single trip.
According to one aspect of the invention, there is provided a method for completing a well comprising the steps of: inserting a completion tool assembly into the well, the completion tool assembly having a gravel packing assembly and a service tool assembly slidably positioned substantially within an interior cavity in the gravel packing assembly; removably coupling the service tool assembly and the gravel packing assembly; inserting a first plugging device into an interior channel within the service tool assembly to substantially block fluid from flowing through the interior channel past the first plugging device; diverting the fluid blocked by the first plugging device through a first fluid flow path to an exterior of the completion tool assembly; gravel packing the well with the completion tool assembly; inserting a second plugging device into the interior channel of the service tool assembly to substantially block fluid from flowing through the interior channel past the second plugging device; diverting the fluid blocked by the second plugging device through a second flow path that reenters the interior channel at a location distal of the first and second plugging devices; and stimulating the well with the well completion assembly.
According to a further aspect of the invention, there is provided a well completion tool assembly for gravel packing and stimulating a well comprising: a gravel packing assembly including a gravel packer; a service tool assembly slidably positioned substantially within an interior channel of the gravel packing assembly and capable of being removably coupled thereto, the service tool assembly including a cross-over tool having a cross-over tool aperture therein, an interior conduit between an annular bypass port into the interior channel located distal of the cross-over tool aperture and a exterior port to an exterior of the service tool assembly located proximal of the cross-over tool aperture, and an annular bypass closing mechanism for selectively opening and closing the annular bypass port.
According to still another aspect of the invention, there is provided a method for completing a well comprising the steps of: inserting into the well a completion tool assembly having a gravel packing assembly having a gravel packer, and a service tool assembly slidably positioned substantially within an interior cavity of the gravel packing assembly and having an interior channel therein; removably coupling the service tool assembly to the gravel packing assembly; setting the gravel packer; obstructing the interior channel with a first obstruction device; opening a first fluid flow path between the interior channel at a location proximal of the first obstruction device and an exterior of the well completion assembly at a location distal of the gravel packer; gravel packing the well with the completion tool assembly by pumping a slurry fluid into a proximal end of the interior channel and through the first fluid flow path; obstructing the first fluid flow path with a second obstruction device to prevent fluid flowing into the proximal end of the interior channel from flowing through the first fluid flow path; opening a second fluid flow path between the interior channel at a location proximal of the second obstruction device and the interior channel at a location distal of the first obstruction device, and stimulating the well with the completion tool assembly by pumping a stimulating fluid through into the proximal end of the interior channel and through the second fluid flow path.
According to another aspect of the invention, there is provided a method for completing a well in a single trip, the method comprising the steps of: inserting a completion tool assembly into the well, the completion tool assembly having a gravel packing assembly and a service tool assembly slidably positioned substantially within an interior cavity in the gravel packing assembly; removably coupling the service tool assembly and the gravel packing assembly; plugging at a first location, whereby fluid is blocked from flowing through the interior channel; diverting fluid blocked by the plugging at the first location through a first fluid flow path to an exterior of the completion tool assembly; circulating a gravel pack slurry through the completion tool assembly; plugging at a second location, whereby fluid is blocked from flowing through the interior channel; diverting fluid blocked by the plugging at the second location through a second flow path that reenters the interior channel at a location distal of the first and second plugging locations; and circulating a filter cake stimulating fluid through the well completion assembly.
BRIEF DESCRIPTION OF THE DRAWINGS
A more complete understanding of the present invention and advantages thereof may be acquired by referring to the following description taken in conjunction with the accompanying drawings, in which like reference numbers indicate like features, and wherein:
FIG. 1 illustrates a typical horizontal well having a filter cake covering a portion of the wellbore wall; (Prior Art).
FIG. 2 is a flow chart illustrating steps for completing a well according to the present disclosure;
FIG. 3 illustrates a well completion tool assembly according to the present disclosure during washdown;
FIG. 4 illustrates a well completion tool assembly according to the present disclosure during setting of the gravel packer;
FIG. 5 illustrates a well completion tool assembly according to the present disclosure during testing of the gravel packer;
FIG. 6 illustrates a well completion tool assembly according to the present disclosure during reversing of the gravel packer;
FIG. 7 illustrates a well completion tool assembly according to the present disclosure during gravel packing; and
FIG. 8 illustrates a well completion tool assembly according to the present disclosure during stimulation of the well.
DETAILED DESCRIPTION
Preferred embodiments of the present invention are illustrated in the Figures, like numeral being used to refer to like and corresponding parts of the various drawings.
Referring now to FIG. 1 , in horizontal wells 101 it is common practice not to form a casing in the well bore 100 along the portion of the horizontal wellbore through which oil or gas 102 is to be extracted. Instead, during drilling operations a “filter cake” 104 is deposited on an inner surface 105 of the wellbore. This filter cake is typically a calcium carbonate or some other saturated salt solution that is relatively fluid impermeable, and therefore, impermeable to the oil or gas in the surrounding formation. The filter cake is formed during drilling by pumping a slurry having particles suspended therein into the wellbore. The particles are deposited on the wellbore surface, eventually forming a barrier that is sufficiently impermeable to liquid. Systems and methods for depositing such a filter cake are well known in the art.
With the filter cake in place, the drilling equipment is removed from the well, and other tools are inserted into the well to pack the well with gravel. Once gravel packing is complete, the filter cake must be “stimulated” with the proper chemical solution to dissolve it to maximize production flow into the well. As indicated above, prior art systems and methods require removal of gravel packing tools and subsequent insertion of stimulation tools. According to the present disclosure, however, a single tool assembly can be lowered into the well to perform both gravel packing and stimulation in one trip.
A system and method for gravel packing and stimulating a well bore will now be described in greater detail with reference to FIGS. 1–8 . According to one embodiment of the present disclosure, a completion tool assembly 301 including a gravel packing assembly 300 and a service tool assembly 330 is run into the well 101 . The gravel packing assembly has an interior cavity 345 extending substantially along its entire length, and a substantial portion of the length of the service tool assembly is slidably positioned within the interior cavity of the gravel packing assembly. The service tool assembly can be retracted relative to the gravel packing assembly as is illustrated in FIGS. 3–8 and as will be described further below Although not explicitly shown in FIGS. 3–8 , it is to be understood that a filter cake has already been deposited along the appropriate portion of the wellbore 101 (step 202 of FIG. 2 ).
The gravel packing assembly includes at a distal end 343 a production screen 306 . The production screen may be a single screen, or preferably multiple production screen sections 306 a interconnected by a suitable sealed joint 380 , such as an inverted seal subassembly. When production begins, the production screen filters out sand and other elements of the formation from the oil or gas. The service tool assembly 330 includes a service string 332 coupled to a cross-over tool 334 . A proximal end 336 of the service tool assembly includes a setting tool 382 that removably couples the service tool assembly to the gravel packer 320 of the gravel packing assembly at the proximal end 346 of the completion tool assembly. The proximal end of the service tool assembly is also coupled to a pipe string (not shown) that extends to the surface of the well for manipulating the service tool assembly.
Cross-over tool 334 is of a type also well known in the art. Cross-over tool 334 includes at least one cross-over tool aperture 350 providing a fluid flow path between the interior channel 338 and an exterior of the cross-over tool. It also includes a separate internal conduits 349 that form a fluid flow path between an annular bypass port 386 that opens into the interior channel at a location distal of the cross-over tool apertures, and an exterior port 399 that opens to the exterior of the cross-over tool at a location proximal of the cross-over tool apertures. With the gravel packing assembly and service tool assembly in position within the wellbore as shown in FIG. 3 , washdown operations ( FIG. 2 , step 204 ) are performed to remove any remaining drilling fluid or debris from the service tool assembly by pumping clean fluid therethrough. The fluid flow path during washdown is illustrated by the arrows in FIG. 3 .
As shown, fluid flows in a substantially unobstructed path through an interior channel 338 in the service tool assembly. The fluid flows out into the well area through a distal aperture(s) 340 at the distal end 341 of the service tool assembly and a distal aperture(s) 342 at the distal end 343 of the gravel packing assembly and well completion tool, and back in the annular space between the completion tool assembly and the wellbore that, before setting of the gravel packer, is present along the entire length of the completion tool assembly. In this manner, the service string assembly and the outer annular area between the gravel pack and screen assembly and the casing/formation are flushed clean of any remaining drilling fluid or debris.
After washdown is complete, gravel packing operations begin, and the completion tool assembly described herein can simply and readily perform both operations. As indicated above, during washdown the interior channel 338 of the service tool assembly is substantially unobstructed. According to the present system and method, a first plugging device 322 is inserted into the interior channel 338 (step 206 ) to form an obstruction and divert the fluid path to enable setting of the gravel packer. The first plugging device may be made of any suitable material and of any suitable configuration such that it will substantially prevent fluid from flowing through the interior channel past the first plugging device. According to one embodiment, the first plugging device is a spherical steel ball. It is inserted into place by dropping it into the annulus of the tool string at the surface of the well, and will travel into the proper position within the service tool assembly by means of gravity and fluid flow. A primary ball seat 398 may also be positioned within the interior channel of the service tool assembly to help retain the first plugging device in the proper position.
As shown in FIG. 4 , the gravel packing assembly has at least one gravel packing aperture therein that, when the service tool assembly is removably coupled to the gravel packing assembly, is aligned with the cross-over tool aperture such that fluid may flow from the interior channel and through both apertures when unobstructed. A temporary closing sleeve 368 , however, controls fluid flow through the gravel packing assembly apertures, and is in the closed position during setting of the gravel packer as shown in FIG. 4 (step 208 ). Thus, during setting, the first plugging device 322 obstructs fluid flow through the interior channel 338 , and because the temporary closing sleeve is also closed, fluid pressure within the interior channel 338 of the service tool assembly builds up in the vicinity of the gravel packer sufficiently to force the gravel packer outwards against the wellbore, thereby setting the gravel packer in place against the wellbore. These techniques are well known in the art, as are standard cross-over tools.
The completion tool assembly of the present invention, however, is also able to maintain annular pressure on the well formation during setting of the gravel packer. The well completion tool assembly includes an annular bypass closing mechanism for selectively opening and closing the annular bypass port. According to one embodiment, this annular bypass closing mechanism includes a device positioned within the interior channel that is slidable relative to the interior channel between open and closed positions. The device is configured so that when in the closed position, it obstructs the annular bypass port, and when slid into the open position it is configured so as not to obstruct the annular bypass port. According to one embodiment, the device is also the primary ball seat. Seating of the first plugging device within the primary ball seat causes the primary ball seat to slide sufficiently so that an opening therein becomes substantially aligned with the annular bypass port 386 so as not to obstruct it. Thus, fluid may freely flow from a first annular space 347 proximal of the gravel packer through the internal cross-over tool channels and into the interior channel at a location distal of the first plugging device. Thus, annular pressure is maintained on the formation to help maintain its integrity prior to gravel pack operations.
Once set, the gravel packer must be tested (step 210 ), and to test the packer the annular bypass port must once again be closed to isolate the annular fluid above the packer. As shown in FIG. 5 , the proximal end 336 of the service tool assembly is uncoupled from the gravel packer 320 , and the service tool assembly is partially retracted from within the gravel packing assembly. This movement of the service tool assembly relative to the gravel packing assembly opens the temporary closing sleeve 368 , thereby allowing fluid flow between the interior channel 338 and the exterior of the gravel packing assembly. Further, this movement also causes a temporary interference collar 390 of the gravel packer assembly to engage a service tool isolation valve 388 that forms part of the service tool assembly. On further retraction of the service tool assembly, the service tool isolation valve stays substantially stationary relative to the gravel packing assembly, causing the annular bypass to once again be obstructed as shown in FIG. 5 by an interference member 400 .
Following testing, the service tool is moved back downward removing the temporary interference collar to once again open the annular bypass 386 as shown in FIG. 6 . Once this is accomplished, the service tool assembly is retracted relative to the gravel packing assembly to a point at which the cross-over tool apertures are positioned proximal of the gravel packer and form a flow path between the interior channel 338 and the first annular space. In this position fluid can be circulated at a point above the packer to avoid unnecessary exposure of the formation to such fluids. Thus, the well completion tool assembly according to the present disclosure is capable of selectively opening and closing the annular bypass port to advantageously maintain annular pressure on the formation and also to prevent pressure surges on the formation prior to and during gravel packing operations.
Subsequently, gravel packing is performed (step 212 ). As shown in FIG. 7 , the service tool assembly is once again removable coupled to the gravel packing assembly by the setting tool 382 . In this position, the cross-over tool apertures 350 again substantially line up with the now open gravel packing apertures 384 . Thus, the fluid slurry used for gravel packing is pumped in through annular channel 338 , and is diverted by the first plugging device 322 through the cross-over tool apertures 350 and gravel packing apertures 384 , and out into the second annular space between the completion tool assembly and the wellbore, where it deposits sand in the production zone. Sand free fluid returns into the lower portion of the interior channel 338 through production screen 306 , passes through the annular bypass port 386 , internal conduit, and exterior port 399 , and into the first annular space.
Once gravel packing is complete, the filter cake must be removed before oil or gas can be extracted from the surrounding formation. According to the present disclosure, the above-described completion tool assembly can also simply and easily perform well stimulation to remove the filter cake while remaining in the well.
As shown in FIG. 8 , a second plugging device 800 is inserted into the interior channel 338 of the service tool assembly to once again divert fluid flow (step 214 ). This second plugging device can be made of any suitable material, i.e., steel, and can be inserted into the service tool assembly in the same manner as described above for the first plugging device. The second plugging device, however, is of a diameter and configuration such that it forms a seal in a section of the interior channel of the service tool assembly that is above or proximal of the cross-over tool apertures 350 , thereby isolating the cross-over tool apertures with plugging devices both above and below.
The interior conduit of the cross-over tool also extends between the annular bypass port and an interior port 349 into the interior channel at a location proximal of the cross-over tool aperture. This interior port is opened by a sleeve which is shifted downward by the second plugging device. This sleeve closes the annular bypass port and opens the interior port. Fluid pumped into the interior channel above the second plugging device is now diverted through the interior port 349 , the interior conduit within the cross-over tool, the annular bypass port, and back into the interior channel 338 at a point below the first plugging device. Thus, fluid will once again flow into the interior channel at a point below or distal of the first plugging device, and the completion tool assembly can now be used to stimulate the well.
Stimulating fluid such as acids or solvents are pumped into the distal end of the interior chamber through the fluid path described above, where it exits the completion tool assembly through the distal apertures 340 in the service tool assembly and the production screen 306 of the gravel packing assembly. The stimulation fluid is diverted through the production screen by slick joints 355 that now seal off flow above and below the production screen. The stimulation fluid reacts with the filter cake on the surrounding wellbore to dissolve it. According to the present embodiment, the filter cake in the proximity of each screen element 306 a , is dissolved one section at a time, optimally starting with the most distal screen section. This is done both to ensure that there is adequate pressure to force the stimulation fluid out into the filter cake, and also to ensure that the filter cake is dissolved in a controlled fashion to prevent leakage before production is ready to begin. The service tool assembly is simply retracted from within the gravel packing assembly to move from one section to the next.
Subsequently, the service tool assembly is removed from the well. As it is removed, flapper valve 310 closes behind it to prevent loss of oil or gas before the production tubing is in place and production is ready to begin.
Although the present invention has been described in detail, it should be understood that various changes, substitutions and alterations can be made hereto without departing from the spirit and scope of the invention as defined by the claims. | A method for completing a well in a single trip, including: inserting a completion tool assembly into the well, the completion tool assembly having a gravel packing assembly and a service tool assembly slidably positioned substantially within an interior cavity in the gravel packing assembly; removably coupling the service tool assembly and the gravel packing assembly; plugging at a first location, whereby fluid is blocked from flowing through the interior channel; diverting fluid blocked by the plugging at the first location through a first fluid flow path to an exterior of the completion tool assembly; circulating a gravel pack slurry through the completion tool assembly; plugging at a second location, whereby fluid is blocked from flowing through the interior channel; diverting fluid blocked by the plugging at the second location through a second flow path that reenters the interior channel at a location distal of the first and second plugging locations; and circulating a filter cake stimulating fluid through the well completion assembly. | 4 |
FIELD OF THE INVENTION
[0001] The present invention relates to a method for preventing the deposition of impurities in steam systems, in which the steam of a given steam quality flowing in them is subjected to temperature and/or pressure changes. The invention also relates to a steam system for carrying out the method.
BACKGROUND OF THE INVENTION
[0002] For the cooling of components subjected to high thermal load in energy machines, for example a gas turbine plant, it is intended, for reasons of efficiency, to make increasing use of steam as a coolant. This steam can flow as steam, but also as a steam/air mixture, in an open, semi-open or closed system through the components to be cooled.
[0003] In an open steam system, the steam is led from a device for the provision of steam (waste-heat boiler, steam turbine plant, auxiliary steam generator, etc.) to the device for the use of steam, for example a gas turbine plant, in order to cool the components of the latter while being heated. The cooling steam, after flowing through the cooling system of, for example, the gas turbine plant, passes into the working medium of the gas turbine plant and ultimately, together with this, into the atmosphere.
[0004] In a semi-open steam system, the steam is led from a device for the provision of steam (waste-heat boiler, steam turbine plant, auxiliary steam generator, etc.) to the device for the use of steam, for example a gas turbine plant, in order to cool the components of the latter while being heated. The cooling steam, after flowing through the cooling system of the gas turbine plant, is supplied to a device for steam take-off (waste-heat boiler, steam turbine plant, technological process, etc.).
[0005] In a closed steam system, the device for the provision of steam (steam cooler, steam blower, steam filter, etc.) is identical to the device for steam take-off. The device for the provision of steam makes steam having the appropriate parameters available to the device for the use of steam, in our case the gas turbine plant. After flowing through the cooling system of the gas turbine plant, the steam is returned to the device for the provision of steam, in order to carry out the pressure rise, cooling, cleaning and the like necessary for maintaining the circulation.
[0006] In the case of steam injection for an increase in power output, steam is injected as an additional working medium into the gas turbine plant in order to increase the mass flow of the working medium. This may, in turn, take place in the form of the direct injection of steam into the working medium or indirectly after the flow through of gas turbine components to be cooled. The steam may, however, also be injected in the form of a steam/air mixture, that is to say in combination with cooling air, into the working medium via an open air-cooling system, again indirectly, that is to say after the flow through of gas turbine components to be cooled.
[0007] The method of steam injection, that is to say steam introduction, into the working medium of the gas turbine plant is also employed in the Cheng cycle. In the Cheng cycle, to avoid the need for a steam turbine plant and the systems necessary for operating the steam turbine plant, the steam generated in the waste-heat boiler is injected completely into the gas turbine plant.
[0008] Impurities in the steam are distinguished by a particular steam solubility. In this context, where possible deposits are concerned, silicon dioxide (SiO 2 ) is particularly important because of the problems involved in the purification of make-up water and condensate and also on account of the difficulties in detection by measurement. SiO 2 will therefore be used below, by way of example, to represent the multiplicity of possible impurities.
[0009] The high-precision components of a gas turbine plant, the small dimensions of the cooling ducts, the stringent requirements to be met by the flow conditions and the like result in the need to ensure a high steam quality. Without this purity, deposits occur within the steam systems, the performance of the plants is diminished and inspections with corresponding shutdown periods of the plants become necessary. This is important, in particular, for the open and semi-open steam systems, because, in these systems, the cooling steam constantly has to be provided anew, and therefore new impurities may always enter the system.
[0010] This results, not least for the steam generator technology employed, in numerous constraints, for example with regard to component design (steam drying in drums and separators), steam temperature regulation by water injection or steam mixing, the chemical operating modes, etc.
[0011] Attempts are being made, at the present time, by appropriate steam provision and steam purification concepts, to ensure a steam quality which avoids deposits with a high degree of reliability. Thus, numerous steam mixing methods are known so the steam temperature can be regulated without water injection. Furthermore, special steam filters, in particular for closed steam systems, are recommended.
[0012] For steam applications of this kind with an adversely high technical and therefore also financial outlay, all these attempts are based on ensuring the generation of very pure water, further improving the quality of this water by means of condensate purification plants, avoiding contamination of the steam by means of appropriate methods of steam generation and steam parameter regulation, freeing the steam of impurities by means of suitable filters and preventing chemical interactions, for example corrosion, in the respective systems by a suitable choice of material.
SUMMARY OF THE INVENTION
[0013] The object on which the invention is based, therefore, is to make available a method for preventing the deposition of impurities in steam systems, in which method the disadvantages of the prior art are avoided.
[0014] The solution according to the invention for achieving the above object, in steam systems of this kind, in which the steam of a given steam quality flowing in them is subjected to temperature and/or pressure changes, is, by an appropriate structural configuration and design of the steam systems, to prevent the steam solubility of the impurities present in specific concentrations in the steam from being exceeded as a result of changes in the temperature and/or pressure conditions.
[0015] The essence of the invention, therefore, is not, as hitherto according to the prior art, to bring the quality, that is to say the purity, of the steam to a specific very low value preventing deposits with high probability, but, instead, under the conditions given in practice for the steam quality and according to the solubility behavior of the impurities, to prevent a situation where a separation of the impurities in a steam system can occur at all. To be precise, it becomes clear, surprisingly, that the total “prepurification” of the water or of the steam is not actually necessary at all, but that it is sufficient to avoid critical parameters being reached in the steam system, that is to say to avoid steam parameters which entail a separation of impurities.
[0016] This is carried out in that, by a suitable choice of the design parameters and/or by an appropriate routing of the steam in the system, or, if appropriate, by appropriately ensuring the temperature, the temperature and pressure parameters never assume values which make a separation of impurities possible. In other words, it is crucial to prevent an excessive lowering of temperature and/or pressure to a critically low value. This may take place in many different ways, either by preventing a critical lowering of the temperature by an increase in the steam mass flow and/or by a reduction in cooling external influences and/or else also by the steam experiencing a corresponding temperature increase, particularly in critical regions of the steam system. Influence can be exerted on the pressure in that, by the type and configuration of steam routing in the steam system, the flow conditions are designed in such a way that pressure losses, particularly in critical regions, are avoided.
[0017] A first embodiment of the method according to the invention is distinguished in that the impurities are silicon dioxide (SiO 2 ).
[0018] In a further embodiment of the method, the method is employed in the case of steam cooling or steam injection of a gas turbine plant. These are two particularly important applications of steam in gas turbine plants.
[0019] Moreover, as an additional measure for the prevention of deposits, there may be provision for the temperature and/or pressure of the steam flowing in the steam system to be set in such a way that the steam solubility of the impurities present in a specific concentration in the steam is not exceeded in the steam system. The latitude for the temperature and/or pressure parameters of the steam flowing in steam systems is usually sufficient to reduce even further the risk of deposits by a specific selection or optimization of at least one of these parameters.
[0020] The method can be organized in a particularly advantageous way in that both values are monitored simultaneously and the pair of values, namely the pressure and temperature of the steam in the steam system, never assumes a critical value, and in that particularly critical regions of the steam system with significant pressure drops are avoided. In particular, this may also be carried out in that a lowering of the pressure such that the steam solubility of the impurities present in specific concentrations in the steam would be exceeded is compensated by means of a corresponding rise in the temperature.
[0021] As regards steam/air mixtures, it must be remembered that, in this case, the partial pressure of the steam in the mixture must be adopted as pressure quantity for the steam pressure.
[0022] A further exemplary embodiment of the invention is characterized in that the sole critical pressure drop in the steam system is placed at the outlet point of the steam from the device for the use of steam. Thus, deposits will occur at most in the outlet region which is easy to clean. If, moreover, the flow velocities of the steam are high at the outlet point, a self-cleaning effect may be established.
[0023] The invention comprises, furthermore, a steam system for carrying out one of the above-described methods.
BRIEF DESCRIPTION OF THE DRAWINGS
[0024] The invention will be explained in more detail below by means of exemplary embodiments in conjunction with the drawings in which:
[0025] FIG. 1 shows a solubility diagram for SiO 2 in water and steam,
[0026] FIG. 2 shows an i,s-graph with lines of constant steam solubility of SiO 2 , and
[0027] FIG. 3 shows an i,s-graph according to FIG. 2 with the parameter profile in a semi-open steam system.
DETAILED DESCRIPTION OF THE INVENTION
[0028] The steam solubility of impurities depends essentially on the pressure and temperature parameters. In general, with a rise in temperature and a rise in pressure, their steam solubility rises and vice versa, the pressure influence being dominant. FIG. 1 shows by way of example for all impurities a diagram for the solubility of SiO 2 in water or steam as a function of the temperature at pressures of 1 bar, 6 bar, 19 bar and 50 bar. It is clear that, for a pressure of 6 bar and a temperature of 400° C., SiO 2 is soluble in steam up to a concentration of approximately 1 mg/kg (1000 ppb).
[0029] In spite of this behavior which is known per se, for the prevention of deposits in steam systems, it has hitherto always been concluded that only by ensuring the conditions corresponding to the most unfavorable case and therefore by the lowest concentration of SiO 2 or of another impurity is it possible for a deposition of this to be effectively prevented. Thus, to avoid SiO 2 deposits in steam systems, concentrations of less than 0.02 mg/kg (SiO 2 <20 ppb) are predetermined as standard values.
[0030] Since the provision of steam of such purity, particularly in open and semi-open steam systems, is costly, the attempt according to the invention is based on avoiding critical pressure and temperature values in the system at which deposits of impurities could occur.
[0031] Temperatures in the range of 250 to 580° C. and pressures in the range of 20 to 40 bar typically prevail in steam systems of gas turbine plants (steam cooling, steam injection, etc.).
[0032] By a gas turbine plant is meant below a plant consisting of at least one compressor, of at least one combustion chamber and of at least one gas turbine. Air is sucked in and compressed by the compressor and is then supplied as combustion air to a combustion chamber, and the hot gas occurring there is expanded in a gas turbine so as to perform work. The at least one gas turbine and the at least one compressor are located on one shaft.
[0033] By virtue of the multiplicity of possibilities resulting from the combination of the steam systems, the function of the steam system, the components through which steam flows and the like in a gas turbine plant, the device for the use of steam may, in a gas turbine plant, be the entire plant, but also, for example, only one component of the casing or a blade row.
[0034] However, the problem of the prevention of deposits is not only relevant to steam systems in which the steam is heated up, as explained by the example of the steam-cooling system of gas turbine plants, but also the use of steam for heating purposes in which the steam experiences a lowering of temperature. By the term “steam system” are therefore meant, in general, steam-cooling systems, but also steam-heating systems.
[0035] FIG. 1 , then, illustrates, furthermore, various parameter changes together with the resulting effects on the steam solubility, again by the example of silicon dioxide (SiO 2 ).
[0036] First, the arrow I illustrates an isobaric transition from a state A with p=6 bar and T=400° C. into a state B with p=6 bar and T=300° C. It can easily be seen that a pressure reduction of this kind may already lead to the separation of SiO 2 . If the maximum SiO 2 concentration soluble in steam amounted at the point A to 1.0 mg/kg (1000 ppb), it fell back to a value of 0.14 mg/kg (140 ppb) at the point B.
[0037] The arrow II illustrates an isothermal transition from the state B into the state C with p=1 bar and T=300° C. It can be seen, again, that a lowering of temperature of this kind may likewise lead to the separation of SiO 2 . When the maximum SiO 2 concentration soluble in steam amounts to 0.14 mg/kg (140 ppb) at the point B, it falls back to a value of 0.11 mg/k (110 ppb) at the point C.
[0038] The arrow III illustrates an isobaric transition from the state C into the state D with p=1 bar and T=500° C. It can be seen, again, that, in contrast to the previous changes of state, a temperature rise of this kind in this case leads to an increase in the steam solubility of SiO 2 . When the maximum SiO 2 concentration soluble in steam amounts to 0.11 mg/kg (110 ppb) at the point C, it rises to a value of 0.18 mg/kg (180 ppb) at the point D. A temperature rise is therefore appropriate for counteracting or compensating a reduction in the steam solubility of the impurities due to a pressure drop.
[0039] By utilizing the solubility behavior of impurities, then, deposits in steam systems can be avoided in that
the design parameters selected for pressure and/or temperature are sufficiently high, care is taken to ensure that the steam solubility of impurities is never reached or exceeded due to a pressure and/or temperature drop, or in that the fall in steam solubility as a result of a pressure drop is partially or completely compensated by a temperature rise.
[0043] According to the invention, then, parameter configurations in steam systems which are critical in terms of possible separations of impurities are avoided in that care is taken, at a process level and flow level, to ensure that the limit for possible separations is never reached or exceeded. This is achieved in that, by means of the system design,
when there is a need to control pronounced pressure and/or temperature drops, the design parameters selected for pressure and/or temperature are sufficiently high, a critical combination of pressure drop and temperature drop is avoided, a critical lowering of the steam solubility as a result of pronounced pressure drops is compensated by a corresponding heating of the steam and consequently a temperature rise.
[0047] Gas turbine plants are employed frequently, virtually without exception in current generation, together with waste-heat boilers. Waste-heat boilers have up to three pressure stages and, possibly, intermediate super heating. There is therefore a multiplicity of possibilities for influencing the parameters of a corresponding steam system.
[0048] Pronounced pressure and/or temperature drops in steam systems can be avoided by means of an appropriate design of the flow cross sections, selection of steam mass flows and the like.
[0049] If, as illustrated by the example of the gas turbine plant, the steam serves for the cooling of components, the steam undergoes heating by heat absorption. Care must be taken, then, to ensure, in structural terms, that appropriate heating of the cooling steam takes place upstream of and/or in regions with a significant pressure drop.
[0050] FIG. 2 shows an h,s-diagram with lines of constant SiO 2 solubility in steam. The steam solubility decreasing with a fall in pressure and a fall in temperature can be seen again. The lines of constant SiO 2 steam solubility interestingly correspond approximately to the angle bisecting line between the lines of constant pressure and the lines of constant temperature. The limit value (GW) for steam turbines is also illustrated.
[0051] FIG. 3 illustrates, additionally to FIG. 2 , the changes of state to the steam within the steam system, in the present case a semi-open steam-cooling system of a gas turbine plant, in the form of an h,s-diagram (x-axis: entropy, y-axis: enthalpy). The cooling steam has a pressure of 30 bar and a temperature of 360° C. at the point E (outlet from the device for the provision of steam). As far as the gas turbine plant or the component to be cooled (device for the use of steam), for example a blade, pressure losses of approximately 8 bar and temperature losses of approximately 5 K occur. The steam therefore has a pressure of approximately 22 bar and a temperature of 355° C. at the point F (inlet into the device for the use of steam). This pressure loss is accompanied by a sharp decrease in steam solubility. During the flow through of the components to be cooled (device for the use of steam), further pressure losses of the order of magnitude of 4 bar occur. However, the steam is heated by approximately 200 K. At the outlet of the component to be cooled, therefore, the steam has a pressure of 18 bar and a temperature of 560° C. at the point G (outlet from the device for the use of steam). With these parameters, then, the steam is supplied to a device for steam take-off. As a result of the temperature rise, there is a marked increase in the steam solubility of SiO 2 within the device for the use of steam. For the process illustrated, to prevent SiO 2 deposits, it will be sufficient to maintain a limit value for the SiO 2 concentration of 3000 ppb (3 mg/kg). It can be seen, furthermore, that the region critical for deposits is the inlet region of the steam into the component to be cooled (device for the use of steam). However, the limit value GW conventionally used for steam systems and specified for steam turbine plants amounts to only 20 ppb.
[0052] Somewhat different conditions arise with regard to steam/air mixtures. In this case, the partial pressure of the steam, dependent on the steam concentration, must be adopted for the steam pressure. There are therefore low partial pressures of the steam, particularly at low steam concentrations, which, in turn may lead to very low steam solubilities of the respective impurity. This can be remedied by maintaining a minimum steam concentration.
[0053] Under the conditions mentioned, it is advantageous to provide a significant pressure drop in the steam system at the point of outlet of the steam from the component to be cooled or from the device for the use of steam and, at the same time, implement as high an outlet velocity of the steam as possible. Consequently, the deposition of impurities, for example as a result of unusual operating conditions, would be concentrated firstly at easily accessible points and therefore points which are easy to clean. Owing to the self-cleaning effect established with an increase in steam velocity, the deposition of impurities can be limited and, in the best possible case, prevented. | In a method for preventing the deposition of impurities in steam systems, in which steam of a given steam quality flowing in them is subject to temperature and/or pressure changes, a simple prevention of deposits is achieved in that an appropriate structural configuration and design of the steam systems prevents the steam solubility of the impurities present in specific concentrations in the steam from being exceeded as a result of changes in the temperature and/or pressure conditions. | 5 |
[0001] This application claims the benefit of U.S. Provisional Application 60/621,941 filed Oct. 26, 2004.
FIELD OF THE INVENTION
[0002] This invention relates to crossbows.
BACKGROUND OF THE INVENTION
[0003] It is well known that crossbows are difficult to cock due to the powerful limbs that are used by this equipment. Over the centuries various apparatus has been developed to provide an easier method for drawing a bow string for engagement with a trigger mechanism. Such devices have included levers, windlasses, built-in pulley systems that are attached to the stock of the bow as well portable rope and pulley means. All of these devices provided some degree of mechanical advantage.
[0004] Earlier attempts to assist with cocking have been overly complex such as those described in related United States patents all by Bednar, being, U.S. Pat. Nos. 6,286,496, 6,095,128 and 6,874,491. These devices preferably are utilized in connection with additional power sources such as hand cranks, powered motors, or powered screwdrivers to assist the user in cocking the crossbow. Redundancy for safety purposes is also not incorporated into these devices.
SUMMARY OF THE INVENTION
[0005] It is an object of the present invention to provide a cocking device that is less expensive to produce than existing systems.
[0006] It is an object of the present invention to provide a cocking device that provides easier storage of the cocking device.
[0007] It is an object of the present invention to provide a cocking device that provides redundancy for safety in the event of breakage of a cable or handle during cocking.
[0008] It is a further object of the present invention to provide a cocking device that is easier to operate than existing devices.
BRIEF DESCRIPTION OF THE DRAWINGS
[0009] In order that the invention may be more clearly understood, the preferred embodiment thereof will now be described in detail by way of example, with reference to the accompanying drawings, in which:
[0010] FIG. 1 is a bottom view, partly in section, showing a crossbow with the cocking device;
[0011] FIG. 2 is a close up side view of the string, handle and pulley;
[0012] FIG. 3 is a bottom view, partly in section, showing both tackles engaged with the string;
[0013] FIG. 4 shows a user cocking a crossbow using the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0014] In order to more clearly understand the present invention part numbers as assigned in the following parts list will be used:
Part Number Description 2 Barrel 3 Prod 4 String 5 Stock 6 Forestock 7 Tackle 8 Handles 9 Opening in Barrel 10 Trigger Latch 11 Cable 12 Spring 13 Trigger Mechanism 14 Stirrup 15 Pulley
[0015] A preferred embodiment of the crossbow-cocking device is illustrated in the drawing figures. The conventional crossbow is shown from different angles, as shown in FIGS. 1 . & 3 . A user is seen utilizing the cocking mechanism of the present invention is FIG. 4 . In FIG. 2 a close up is shown of the handles 8 and tackles 7 , as stored.
[0016] Such a conventional crossbow has a stock with a first end and a second end, a first side and a second side, and prods or limbs 3 attached proximal to the first end of the main beam or barrel that is mounted within the stock 5 . A string 4 is attached to the prod or limbs and a trigger mechanism 13 located intermediate the first end and the second end of the stock and beam combined length.
[0017] The cocking device is comprised of a pair of guide means each of which have an attaching means, also called tackles 7 , attached to the barrel 2 , as in FIG. 1 . for removable attachment to the bowstring. Both guide means engage a cord or the like, that has a first and a second end. Each guide means is retractably connected to a cable 11 uncoiled and straight as possible or rope that has been attached to a compact constant force spring 12 for retraction when not in use. Within the barrel 2 of the cross bow the cable 11 or rope has been attached to one of the ends of a constant force spring 12 or other means for retracting.
[0018] By generally simultaneously pulling handles 8 on the first and second ropes or cables the cocking means is extracted at point 9 from the barrel 2 and stretched toward the string 4 of the crossbow. Once the block and tackle are attached to both sides of the crossbow string ( FIG. 4 ) the operator bends down toward the handles 8 , grabs them, and pulls them toward himself while bending upward making sure his foot is in the stirrup 14 . This procedure stretches the string to a point that it is able to engage the trigger latch 10 within the barrel that is located between the first and the second end of the said crossbow leaving it in a state ready to be fired or discharged.
[0019] The typical crossbow generally consists of longitudinally extending main beam, or barrel member 2 and two outwardly extending limb members or member 3 , which extend transversely on opposite sides from main beam or barrel member. The crossbow bowstring 4 is strung between the distal ends of outwardly extending limbs 3 . Stock generally includes a rear portion or tailstock 5 having an integrally formed butt portion that is normally positioned against the user's shoulder when crossbow is being aimed and/or fired. The stock further includes a forestock 6 for holding the main beam or barrel 2 , which may be integral to the tailstock 5 , or may be provided as a separate member secured therewith.
[0020] In the preferred embodiment shown, the barrel 2 is a separate member which may be formed of a strong but lightweight material such as aluminum. Extruded aluminum allows for the mounting of the cocking system that resides in the hollow chamber or chambers of the extrusion.
[0021] In one example of this invention the cocking device is comprised of a pair of guide means shown generally as handles (left and right) and removable hooks 7 and pulley 15 , also referred to as block and tackle 7 . As can be seen more clearly in FIG. 1 . the pulley is comprised of a block and a sheave 7 . In the preferred embodiment the main beam or barrel 2 is formed from aluminum but may be made from any suitable material. A cord or cable 11 is provided having a first end and a second end, as illustrated in FIG. 1 & FIG. 3 . FIG. 3 shows the first end of the cable 11 passing through the pulley 15 of the guide means or block and tackle 7 and attached thereafter to a handle 8 to aid in the cocking process. The other end of cable 11 enters the barrel 2 on opposing sides of the same at 9 somewhat rear of the string latching means 10 , from the out side of the barrel 2 continuing to the inside of the extrusion or other and attached thereto 12 .
[0022] In the preferred embodiment a constant force spring 12 is used due to its compact size and its excellent characteristics of equal not increasing force throughout its extension, as would be found in extension of coil springs, elastic or surgical tubing as well, gas or air filled shocks and lastly a spring loaded hub that usually includes a clock type spring that has an increase force as it is wound and needs ample space for mounting or installation of such a hub system.
[0023] Handle 8 is attached for removable attachment to 16 the two are of equal shape in tapered dimensions like male and female, the handle 8 is larger dimensionally than 16 . Both have a complimenting taper with the greater of the tapers facing the butt end, thus the handles are secure due to the fit and secondly by the constant force spring that has a constant force on them in the direction of the larger tapers.
[0024] In the operating position as seen in FIG. 2 . each guide means 7 is removed from holder 16 that is attached to 2 and pull extracted from hole 9 . Once the length of cable is extracted from the barrel or main beam 2 where it resides when not in use, the hooks or block and tackle 7 are extended toward the prod 3 and attached to the bow string 4 . Each hook is attached at a point adjacent to opposing sides of the barrel. The handles 8 one per side as illustrated are pulled in both hands on separate sides of this barrel with your foot in 14 , the mechanical advantage of the pullies which in this case is 50% between the pair of guide means.
[0025] In the preferred embodiment the cord is made from woven nylon fibers; however, the cord may be constructed of any suitable material, as well using the one pulley per side we have a mechanical advantage of 50%. Anyone skilled in this art would be able to accommodate a multiple pulley system with increased mechanical advantage that could also be used in the extruded chambers; one could also reverse the whole assembly to operate from the opposite end.
[0026] It will thus be seen that the objects set forth above, among those made apparent from the preceding description, are efficiently attained and, since certain changes may be made in the above article without departing from the scope of the invention, it is intended that all matter contained in the above description or shown in the accompanying drawings shall be interpreted as illustrative and not in a limiting sense. | The present invention provides a crossbow stringing and cocking device whereby one person may easily and safely draw back the string of a crossbow to engage the trigger mechanism for shooting of a projectile, and may also be utilized to unstring and string the bow. The invention utilizes a pulley system, mounted inside the barrel for convenience and safety. | 5 |
[0001] This application is a Continuation-In-Part of my patent application Ser. No. 11/161,893, filed on Aug. 22, 2005.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to bill dispensers and more particularly, to such a single-bill output control of a bill dispenser, which dispenses only one single bill at a time.
[0004] 2. Description of the Related Art
[0005] Following fast development of modern technology, our mode of living has been changed. Various automatic vending machines (ticket venders, coin exchanging machines, etc.) are used everywhere to sell different products without serviceman. These automatic vending machines save much labor and bring convenience to people. An automatic vending machine may be quipped with a bill dispenser to dispense bills (cards, tickets, coupons, banknotes, etc.). However, due to thin thickness of bills, bills may be not smoothly dispensed, or two or more bills may be overlapped and delivered to the bill outlet at a time. Manufacturers are trying hard to design bill dispensers that can dispense bills smoothly and individually.
[0006] FIG. 8 is a schematic side view of a bill dispenser according to the prior art. As illustrated, the bill dispenser A comprises an accommodation chamber A 1 , a gap adjustment device B disposed at the front side of the accommodation chamber A 1 , a plurality of sheet transferring rollers A 2 disposed at the bottom side of the accommodation chamber A 1 , a motor A 3 controlled to rotate the sheet transferring rollers A 2 and to transfer bills C out of the accommodation chamber A 1 to the bill path controlled by the gap adjustment device B. According to this design, the circumferential length of the sheet transferring rollers A 2 is shorter than the length of the bills C, and the sheet transferring rollers A 2 are molded from a material having a high friction force, for example, rubber. Therefore, the sheet transferring rollers A 2 keep transferring bills C forwards when rotated. To control dispensing of one single bill C at a time, the ratio between the circumferential length of the sheet transferring rollers A 2 and the length of the bills C must be measured. However, this limitation does not allow the bill dispenser to dispense different sizes of bills C. Further, the sheet transferring roller A 2 transfer bills C by means of a friction force. However, due to precision reason, the gap adjustment device B may no adjust a gap of the bill path to fit the thickness of one single bill C precisely. In this case, two overlapped or stacked bills C may be dispensed. If the gap of the gap adjustment device B allows only one single bill C to pass, follow-up bills C may be jammed in the gap adjustment device B or in between the gap adjustment device B and the accommodation chamber A 1 , resulting in failure in functioning of the bill dispenser A.
[0007] Therefore, it is desirable to provide an individual bill output control method for bill dispenser that eliminates the aforesaid problems.
SUMMARY OF THE INVENTION
[0008] The present invention has been accomplished under the circumstances in view. It is therefore the main object of the present invention to provide a bill dispenser, which dispenses one single bill accurately at a time.
[0009] To achieve this and other objects of the present invention, the bill dispenser comprises a housing, which comprises a frameboard, a bill chamber defined above the frameboard, an accommodation chamber defined below the frameboard, a bill outlet in the front side, a bill passage in communication between the bill chamber and the bill outlet, a bill-empty sensor mounted in the frameboard and adapted for providing a bill-empty signal when the bill chamber is empty, a transferring roller set mounted in the accommodation chamber and adapted for transferring bills out of the bill chambers toward the bill passage, a dispensing roller set mounted in the bill chamber between the frameboard and the bill passage and adapted for dispensing bills been transferred by the transfer roller set, an optical transmitter module adapted for transmitting a light across the bill passage when the dispenser roller set is dispensing a bill through the bill passage toward the bill outlet, an optical receiver module adapted for receiving the light that is transmitted by the optical transmitter module and passing through the bill being dispensed through the bill passage toward the bill outlet by the dispensing roller set and outputting an output signal indicative of the intensity of the light received, and a control circuit adapted for receiving the output signal of the optical receiver module and comparing the output signal of the optical receiver module with a predetermined reference value and controlling the operation of the dispensing roller set and the transferring roller set subject to the comparison result.
BRIEF DESCRIPTION OF THE DRAWINGS
[0010] FIG. 1 is an elevational view of a bill dispenser according to the present invention.
[0011] FIG. 2 is an exploded view of the bill dispenser according to the present invention.
[0012] FIG. 3 is a schematic side view in an enlarged scale of a part of the bill dispenser according to the present invention.
[0013] FIG. 4 is a circuit diagram of the control circuit of the bill dispenser according to the present invention.
[0014] FIG. 5 is a schematic sectional side view of the bill dispenser before dispensing of a bill.
[0015] FIG. 6 is similar to FIG. 5 but showing a bill dispensed to the bill outlet.
[0016] FIG. 7 is an operation flow chart of the present invention.
[0017] FIG. 8 is a schematic side view of a bill dispenser according to the prior art.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
[0018] Referring to FIGS. 1-3 , a bill dispenser is shown comprising a housing 1 , an optical receiver module 2 and an optical transmitter module 3 .
[0019] The housing 1 is comprised of a bottom shell 101 , two side panels 102 and a top cover 103 . The housing 1 houses a frameboard 11 . The frameboard 11 has a plurality of slots 111 cut through the top and bottom walls thereof, and two upright locating plates 112 symmetrically disposed at two opposite sides. The housing 1 defines a bill outlet 15 in the front side, a bill chamber 12 above the frameboard 11 for accommodating a number of bills of one single denomination, an accommodation chamber 13 below the frameboard 11 , and a bill passage 14 in communication between the bill chamber 12 and the bill outlet 15 for guiding one single bill out of the bill chamber 12 to the bill outlet 15 at a time. Further, a bill-empty sensor 113 is installed in the frameboard 11 and adapted for providing a bill-empty signal when the bill chamber 12 is empty.
[0020] The optical receiver module 2 is mounted in the housing 1 adjacent to the bill outlet 15 , for example, at a location beneath the bill passage 14 , and comprised of resistors, capacitors, phototransistors and an optical receiving device 21 . Further, the optical receiver module 2 is electrically connected to a control circuit (see FIG. 4 ).
[0021] The optical transmitter module 3 is mounted in the housing 1 adjacent to the bill outlet 15 , for example, at a location above the bill passage 14 , and comprised of resistors, capacitors, phototransistors and an optical transmitting device 31 . Further, the optical transmitter module 3 is electrically connected to the control circuit (see FIG. 4 ). The control circuit controls the electric current going through the optical transmitting device 31 , thereby controlling the intensity of the light emitted by the optical transmitting device 31 . The light emitted by the light transmitting device 31 goes across the bill passage 14 toward the optical receiving device 21 , causing the optical receiving device 21 to output a signal to the control circuit for comparison with a reference value.
[0022] The bill dispenser further comprises a transferring roller set 4 and a dispensing roller set 5 . The transferring roller set 4 is mounted in the accommodation chamber 13 below the frameboard 11 , comprising a number of transferring rollers 41 and an auxiliary roller 42 . Some transferring rollers 41 are provided with a respective push block 411 . The push blocks 411 are movable through the slots 111 into the bill chamber 12 . The dispensing roller set 5 is mounted in the bill chamber 12 between the frameboard 11 and the bill passage 14 . The dispensing roller set 5 is mounted in the bill chamber 12 above the frameboard 11 , comprising dispensing rollers 51 , adjustment rollers 52 and pressure rollers 53 . The dispensing rollers 51 , the adjustment rollers 52 and the pressure rollers 53 are for contacting the periphery of the transferring rollers 41 . The adjustment rollers 52 can be moved vertically to adjust a gap between the respective adjustment rollers 52 and the respective transferring rollers 41 .
[0023] Further, the optical receiver module 2 , the optical transmitter module 3 , the transferring roller set 4 , the dispensing roller set 5 and the control circuit (see FIG. 4 ) are electrically coupled to a drive (not shown), so that the control circuit controls the optical receiver module 2 and the optical transmitter module 3 to operate subject to the setting of a predetermined program, and drives the transferring roller set 4 and the dispensing roller set 5 to carry bills and to dispense bills. Further, the housing 1 can be connected to a host (not shown), enabling the host (computer, bill exchange machine or automatic vending machine) to control the operation of the control circuit (see FIG. 4 ).
[0024] Referring to FIGS. 3, 5 and 6 , a stack of bills 6 of one denomination is placed in the bill chamber 12 inside the housing 1 . When dispensing a bill, the transferring roller set 4 is rotated clockwise. During rotation of the transferring rollers 41 and the auxiliary roller 42 , the push blocks 411 are moved with the respective transferring rollers 41 to rub against the first bill 6 , moving the bills 6 out of the bill chamber 12 to the dispensing rollers 51 of the dispensing roller set 5 toward the bill outlet 15 . When a number of bills 6 reached the dispensing rollers 51 , the dispensing rollers 51 stop the bills 6 into a stepped stack, and move the stepped stack of bills 6 to the pressure rollers 53 , for enabling the bills 6 to be dispensed through the gap between the adjustment rollers 52 and the corresponding transferring rollers 41 into the bill passage 14 . At this time, the optical receiver module 2 and the optical transmitter module 3 are driven to operate.
[0025] When bills 6 are accommodated in the bill chamber 12 , the bill-empty sensor 113 is forced downwards by the accommodated bills 6 . When the bill chamber 12 is empty, the bill-empty sensor 113 receives no pressure, thereby outputting a signal indicative of the empty status of the bill chamber 12 .
[0026] Referring to FIG. 7 , during operation of the optical receiver module 2 and the optical transmitter module 3 , the control circuit (see FIG. 4 ) runs subject to the steps as follows:
[0027] ( 101 ) Start system initialization.
[0028] ( 102 ) Judge whether or not a bill 6 is been dispensed? And then proceed to step ( 103 ) when positive, or step ( 102 ) when negative.
[0029] ( 103 ) The optical transmitter module 3 transmits light toward the bill 6 passing through the bill passage 14 , and the optical receiver module 2 receives the transmissive light from the bill 2 . And then proceed to step ( 104 ).
[0030] ( 104 ) Compare the value of the transmissive light received by the optical receiver module 2 with a predetermined reference value, and then proceed to step ( 105 ) if the difference of the comparison result is within a predetermined range, or proceed to step ( 106 ) if the difference of the comparison result surpasses the predetermined range.
[0031] ( 105 ) The optical transmitter module 3 and the optical receiver module 2 keep detecting whether or not there is any bill 6 been dispensed? And then proceed to step ( 108 ) if positive, or step ( 106 ) if negative (beyond a predetermined length of time).
[0032] ( 106 ) Reverse the dispensing roller set 5 to return the dispensing bill 6 , and then proceed to step ( 107 ).
[0033] ( 107 ) Shut down the machine for troubleshooting.
[0034] ( 108 ) End.
[0035] As stated above, the invention uses an optical transmitter module 3 and an optical receiver module 2 to measure the transmittance of the light passing through the bill 6 that is being delivered through the bill passage 14 for comparison with a predetermined reference value. When two or more bills 6 are delivered through the bill passage 14 , the transmittance of the light passing through the bills 6 shows a significant difference relative to the predetermined reference value, and the control circuit will immediately reverse the dispensing roller set 5 to return the bills 6 .
[0036] Further, the aforesaid reference value can be the transmittance of one single bill. Alternatively, the reference value can be the mean value of the transmittance of every single one of a predetermined number of bills been dispensed through the bill dispenser, then the reference value is programmed in the setting program of the control circuit.
[0037] Although a particular embodiment of the invention has been described in detail for purposes of illustration, various modifications and enhancements may be made without departing from the spirit and scope of the invention. Accordingly, the invention is not to be limited except as by the appended claims. | A bill dispenser is disclosed to include an optical transmitter module and an optical receiver module for measuring the transmittance of the bill being dispensed toward the bill outlet, and a control circuit for comparing the transmittance measured by the optical receiver module with a reference value and controlling the operation of the dispensing roller set of the bill dispenser subject to the comparison result, assuring accurate dispensing of one single bill at a time. | 6 |
TECHNICAL FIELD
[0001] The present invention relates in general to a fibre dewatering press and in particular to arrangement for removing a fibre web from a wire in a wire press.
BACKGROUND
[0002] Dewatering presses for dewatering of a fibre suspension and forming of a continuous web thereof are previously known. One example of a known dewatering press is a twin-wire press, see e.g. the published international patent application WO 2008/105706. Dewatering of the pulp is usually done from an inlet pulp concentration of 3-8% by weight to an output pulp concentration of 30-50% by weight. According to the state of the art, such twin-wire presses comprises two endless wires cooperating for dewatering fibre suspensions provided between them. The fibres form a continuous fibre web provided at an outlet from the twin-wire press.
[0003] When the continuous fibre web leaves the twin-wire press, the wires are fed back into the press while the continuous fibre web is supposed to be released from the wires. In order to ensure that parts of the fibre web do not follow the wires back in to the twin-wire press, doctor blades are typically provided at the surface of the wires at the outlet from the twin-wire press. It is desired that the doctor blade follows the surface of the wire in close proximity when there is a potential risk for fragments of the fibre web to follow the wire. However, the roll driving the wire, which roll typically is made of a relatively soft rubber material, is easily worn. After some operation time, the roll presents a worn and uneven surface. Consequently, the wire that is formed according to the roll surface therefore also often exhibits an uneven surface, even if the wire itself is undamaged. A doctor blade originally mounted in close proximity to the original wire surface is thereby separated from at least parts of the wire surface. Also, if the doctor blade is pushed against such an uneven surface, the doctor blade may damage the raised parts of the wire. The operating conditions at this position are also relatively demanding. The temperature is often in the range of 70-90° C. and may vary with time and the environment typically comprises peroxides. In order to reduce the wear of the wire and at the same time withstand the demanding conditions, the doctor blade is typically made of a polymer material, typically a high-molecular polythene material. Furthermore, at these temperatures, plastic deformation of the material is not unusual as well as displacements resulting from changing temperatures in different parts of the press.
[0004] A general problem in prior art is that the doctor blade arrangements cause too much wear on the wire and/or cannot compensate for worn wires, doctor blade deformation or shifting surrounding temperatures.
RELATED ART
[0005] Doctor blades as such are also utilized e.g. in connection with paper machines, such as e.g. disclosed in the U.S. Pat. No. 1,566,358 or 2,914,788. However, the fibre web in a paper machine is considerably lighter than for pulp applications. In pulp applications, the basis weight is typically higher than 1000 g/m 2 . Furthermore, also other conditions differ considerable between pulp and paper applications. Fibre webs of different weights and at different conditions will behave very differently and doctor blade solutions found in paper manufacturing applications cannot without careful modifications be utilized for pulp manufacturing purposes.
SUMMARY
[0006] An object of the present invention is therefore to provide a doctor blade arrangement presenting low wear on the wire, well adapted resilience behaviour and suitable scraping properties.
[0007] The above objects are achieved by arrangements and methods according to the enclosed patent claims. In general words, in a first aspect, an arrangement for removal of a fibre web from a fibre conveying support comprises a doctor beam and a doctor blade having a web contacting edge. The fibre web has a basis weight over 1000 g/m 2 . The doctor blade and the doctor beam are attached to each other by a pivotable attachment. The arrangement further comprises a hose for fluids arranged for applying a force between the doctor beam and the doctor blade at a distance from the pivotable attachment when being pressurized to move the web contacting edge towards the fibre conveying support by pivoting the doctor blade relative to the doctor beam.
[0008] In a second aspect, a twin-wire press for dewatering of a fibre suspension, comprising lower rolls, an endless lower wire, upper rolls and an endless upper wire, and an arrangement according to the first aspect arranged for removal of a fibre web from at least one of the endless upper wire and the endless lower wire.
[0009] In a third aspect, a method for operating an arrangement for removal of a fibre web from a fibre conveying support comprises pressurizing of a hose for fluids arranged for applying a force between a doctor beam and a doctor blade at a distance from a pivotable attachment between the doctor beam and the doctor blade to move a web contacting edge of the doctor blade towards the fibre conveying support by pivoting the doctor blade relative to the doctor beam. The method further comprises controlling of the pressurizing dependent on an operating condition of a device providing the fibre web.
[0010] One advantage with the present invention is that the wear on doctor blades and fibre conveying supports are significantly lowered.
BRIEF DESCRIPTION OF THE DRAWINGS
[0011] The invention, together with further objects and advantages thereof, may best be understood by making reference to the following description taken together with the accompanying drawings, in which:
[0012] FIG. 1 is a schematic illustration of a twin-wire press;
[0013] FIG. 2 is a schematic illustration of an embodiment of a doctor arrangement according to the present invention;
[0014] FIG. 3 is a schematic illustration of the embodiment of FIG. 2 with pressurized hose;
[0015] FIG. 4 is a block diagram of an embodiment of a twin-wire press arrangement according to the present invention;
[0016] FIG. 5 is a flow diagram of steps of an embodiment of a method according to the present invention; and
[0017] FIG. 6 is a schematic illustration of another embodiment of a doctor arrangement according to the present invention.
DETAILED DESCRIPTION
[0018] Throughout the drawings, the same reference numbers are used for similar or corresponding elements.
[0019] FIG. 1 illustrates schematically a twin-wire press 1 . The illustration is very simplified in order to facilitate the understanding of the general principle. The twin-wire press 1 comprises an endless upper wire 6 A running in a path around upper rolls 8 A. The twin-wire press 1 also comprises an endless lower wire 6 B running in a path around lower rolls 8 B. A fibre suspension is entered into the space between the endless upper wire 6 A and the endless lower wire 6 B through a headbox 10 at an inlet 2 of the twin-wire press 1 . The flow path of fibre suspension/web is indicated by the arrows 5 . The fibre suspension is thus provided into a space 14 between the endless upper wire 6 A and the endless lower wire 6 B. The two wires 6 A, 6 B cooperate with each other through a dewatering section 20 of the path 5 , in which the wires 6 A, 6 B form a wedge-shaped dewatering space for the fibre suspension between each other. During displacement of the wires 6 A, 6 B through the dewatering section 20 , the wires 6 A, 6 B thus successively compress the fibre suspension in the wedge-shaped space, whereby the fibre suspension is initially pressed and dewatered and formed to a continuous fibre web between the wires 6 A, 6 B. At an outlet 3 from the twin-wire press 1 , the fibre web is released from the wires 6 A, 6 B and collected in a shredder 12 . Doctor arrangements 30 are provided at the surface of the wires 6 A, 6 B at a respective roll 8 A, 8 B.
[0020] At the outlet from the twin-wire press 1 , the fibre web is peeled off from the wires. In most situations, the fibre web is uniting in itself and the fibre web is typically released from the wires without problems. However, at some occasions, e.g. when starting or stopping the twin-wire press or when disturbances normal operation conditions appear, there might be portions (or even the entire web) which continue to follow one of the wire surfaces instead of being released. If such fibre material portions are allowed to follow the endless wire into the interior of the twin-wire press again, this can cause serious problems. A doctor arrangement 30 is therefore typically provided in connection with the outlet 3 from the twin-wire press 1 . As described in the background section, prior art doctor arrangements have a number of drawbacks. The doctor arrangement 30 is provided at least one of the wires 6 A, 6 B, and typically at both.
[0021] One embodiment of an arrangement for removal of a fibre web from a wire according to the present invention is illustrated in FIG. 2 , i.e. a doctor arrangement 30 . A roll 8 drives a fibre conveying support 21 , in this embodiment an endless wire 6 , in a conveying direction 26 . In other embodiments, the fibre conveying support 21 could e.g. be the surface of a roll. A fibre web, in this embodiment a web of cellulose pulp, is intended to be conveyed on a surface 24 of the endless wire 6 and be released therefrom before the endless wire 6 returns into the interior of the twin-wire press. The doctor arrangement 30 comprises a doctor blade 32 attached to a doctor beam 34 . The doctor blade 32 is provided for prohibiting any parts of the fibre web to follow the fibre conveying support beyond the outlet 3 . The doctor blade 32 is mechanically supported by the doctor beam 34 , and the doctor beam 34 constitutes the attachment of the doctor blade 32 to the main fibre handling equipment, i.e. in this embodiment the twin wire press. In this embodiment, a portion of the doctor beam is formed as a clamping plate 36 , which clamps the doctor blade 32 against the doctor beam 34 with a pivoting point 35 . The clamping plate 36 is firmly attached to the main part of the doctor beam 34 , in this embodiment by bolts 38 . The clamping plate 36 is in the present embodiment bent in such a way that outside the pivoting point 35 , there is a distance 39 between the doctor blade 32 and the clamping plate 36 , which allows the doctor blade to pivot out from the doctor beam surface around the pivoting point 35 . The clamping plate 36 and the end of the doctor beam 34 thus together form a pivotable attachment 37 of the doctor blade 32 .
[0022] The doctor arrangement 30 is preferably originally mounted in such a way that a web contacting edge 33 of the doctor blade 32 is placed just at the surface 24 of the wire 6 , when the doctor blade 32 is positioned along the surface of the doctor beam 34 . When surrounding conditions are changed, e.g. due to wear of the roll 8 or wire 6 , different temperatures or plastic deformation of the doctor blade, a slit may be left between the web contacting edge 33 and the surface 24 of the wire. For such occasions, a hose 40 for fluids is provided in a recess 41 of the doctor blade 32 . The hose 40 can generally be pressurized with any fluid-gas or liquid and is therefore adapted for being connected to a hose pressurizing arrangement. In the present embodiment, the hose 40 is intended to be pressurized by air.
[0023] FIG. 3 illustrates a situation when the hose 40 is pressurized by a (not shown) hose pressurizing arrangement. The hose 40 expands and protrudes outside the recess 41 and applies a force onto a support surface 42 of the doctor beam 34 . This support surface 42 can be a portion of the main doctor beam 34 itself or be a portion provided with a surface coating adapted for interaction with the expanded hose 40 . In general words, the hose 40 is arranged for applying a force between the doctor beam 34 and the doctor blade 32 at a distance from the pivoting point 35 when being pressurized. The rear end of the doctor blade 32 is thereby moved out from the surface of the doctor beam 34 , leaving a space 43 there between. This force acts to move the web contacting edge 33 towards the fibre conveying means 21 , in this embodiment the wire 6 . The web contacting edge 33 is thereby held against the surface 24 of the wire 6 with a force that is determined by the pressure applied in the hose 40 . The pivoting of the doctor blade 32 is typically limited by the distance 39 to the clamping plate 36 . The web contacting edge 33 follows the surface 24 of the wire 6 even if the roll or wire is unevenly worn. Also mechanical movements in the doctor arrangement 30 as a result of e.g. temperature differences are compensated by such an arrangement. Furthermore, if the doctor blade 32 itself, which typically is made of high-molecular polythene, undergoes plastic deformation, also this is compensated. The doctor blade 32 is preferably manufactured in a material that is relatively soft, such as e.g. high-molecular polythene, which allows the doctor blade 32 to adapt and/or be worn according to the surface profile of the wire and/or roll.
[0024] Now returning to FIG. 2 . When the rather thick fibre web comes into contact with the doctor blade 32 that is gently pressed against the wire 6 , the fibre web also creates a force F on the doctor blade 32 . This force F increases the pressure on the web contacting edge 33 against the surface 24 of the wire 6 . The doctor blade 32 wants to rotate around the pivot point 35 . A higher normal force N is thereby obtained, which increases the friction force R from the wire 6 . The higher the force F becomes the better and tighter the doctor blade 32 is pressed against the wire 6 , and the doctor blade 6 doctors away the fibre web from the wire. Because of this function, there is only need of a small pressure in the hose 40 at normal running to keep the doctor blade 32 close to the wire 6 . Such a lower pressure gives a lower friction and longer lifetime of the wire 6 and doctor blade 32 .
[0025] Thus, during the majority of the operation time of a twin-wire press, the release of the fibre web, i.e. in this case the release of a pulp mat, functions without any need for assistance from any fluid loaded doctor arrangements. During such periods, it would therefore be beneficial if the doctor blade 32 is not actively pressed against the wire 6 surface. As mentioned above, this could reduce the wear both on the wire 6 and/or roll 8 and on the doctor blade 32 . There is thereby a need for being able to control the pressurizing of the hose 40 depending on the actual operating conditions of the twin-wire press.
[0026] The upper doctor blade of a twin-wire press is typically in no contact with the pulp mat when the machine is running. The doctor blade only picks up or pulls out small amount of fibres that is stuck into the wire. The smaller fibre particles more or less follow the wire, even if the doctor blade has loosened the fibre from the wire. Spraying systems are typically provided to handle these particles later.
[0027] Also the lower doctor blade is in no contact to the pulp mat when the machine is running properly. The pulp mat structure and its own weight is pulling the pulp mat out from the wire so that the doctor blade goes free without contact to the pulp mat.
[0028] This typical phenomenon occurs in particular with pulp mats that has a sufficient strength and weight, and it is presently believed that it is a requirement to have a basis weight that is over 1000 g/m 2 , and preferably over 1200 g/m 2 , to achieve this phenomenon. In start up processes and shut down processes of the machine, often both the upper and lower doctor blades are in contact with the pulp mat. Then there is a need to have a strong doctor blade, but made of a gently material for reducing the damage on the wire. This is because the high contact forces that this thick pulp mat generates. The minimum basis weight for pulp mats produced by twin-wire presses is 1200 g/m 2 , which makes the present doctor blade arrangements according to the present invention particularly suitable.
[0029] A further advantageous function for the lower doctor blade arrangement is to provide for a contact between the pulp mat and the clamping plate. This stabilizes the pulp mat on its way to the shredder screw. Without this contact, the pulp mat is more easily broken because of the action of the forces that are applied at the shredder screw and from the weight itself. When a break occurs, the pulp mat looses the force from its own weight that pulls out the pulp mat and there is typically a doctor blade contact against this very thick pulp mat that gives more fibre losses and wearing on the doctor blade. Typically, the speed of the wire is in the range of 10-40 m/min at normal operation.
[0030] A fibre handling system according to an embodiment of the present invention is illustrated in FIG. 4 . A twin-wire press 1 for dewatering of a fibre suspension has doctor arrangements 30 , e.g. according to the embodiment of FIGS. 2 and 3 , mounted at the outlet from the twin-wire press 1 . A hose pressurizing arrangement 50 is connected to a hose of the doctor arrangements 30 . A controller 52 is arranged for controlling the hose pressurizing arrangement 50 . The controller 52 is connected for receiving information about the operation conditions of the twin-wire press 1 . Based on this information, the controller 52 can pressurize the hoses of the doctor arrangements 30 when needed, e.g. during starting or stopping of the twin-wire press 1 , or when other disturbances in the operation is detected. During normal operation of the twin-wire press 1 , the controller 52 can instead allow a release of the pressure and thereby allow the doctor blade to pivot out from the wire surface.
[0031] FIG. 5 illustrates a flow diagram of steps of an embodiment of a method according to the present invention. A method for operating an arrangement for removal of a fibre web from a wire starts in step 200 . In step 210 , a hose for fluids is pressurized. The hose is arranged for applying a force between a doctor beam and a doctor blade at a distance from a pivotable attachment between the doctor beam and the doctor blade to move a web contacting edge of the doctor blade towards the wire. The pressurizing is in step 212 controlled dependent on an operating condition of a device providing the fibre web. The procedure ends in step 299 .
[0032] The embodiment illustrated in FIGS. 2 and 3 has the hose provided in a recess in the doctor blade and arranged to actuate on the doctor beam. Furthermore, the hose applies the force on the doctor blade at a side opposite to the web contacting edge relative to the pivotable attachment 37 and pivoting point 35 . However, there are also alternative embodiments. One alternative embodiment is illustrated in FIG. 6 . Here, the hose 40 is provided in a recess 41 in the doctor beam 34 instead. The hose 40 is thereby arranged to actuate on a support surface 42 at the doctor blade 32 . In another alternative embodiment the hose 40 can be provided such that the hose applies the force on the doctor blade at a same side as the web contacting edge relative to the pivotable attachment.
[0033] The clamping of the doctor blade 32 to the doctor beam 34 at limited areas gives rise to a simple embodiment of a pivotable attachment. Anyone skilled in the art realizes that also other types of pivotable attachments can be utilized, such as different kinds of hinges.
[0034] In the embodiments above, the fibre conveying support is exemplified by a wire. However, the present ideas also operate well with also other types of fibre conveying support, such as e.g. different kinds of rolls.
[0035] The conditions at the outlet from a fibre web handling arrangement, such as a twin-wire press, are relatively special. The environment is hazardous, typically comprising peroxides. At the same time, the temperatures are often in the range of 70-90° C., but may also vary considerably, in particular at starting and stopping the fibre web handling arrangement. The presented solutions are well adapted to withstand such environments at the same time as they provide for simple and cost-efficient operation.
[0036] The embodiments described above are to be understood as a few illustrative examples of the present invention. It will be understood by those skilled in the art that various modifications, combinations and changes may be made to the embodiments without departing from the scope of the present invention. In particular, different part solutions in the different embodiments can be combined in other configurations, where technically possible. The scope of the present invention is, however, defined by the appended claims. | Apparatus for removing fiber webs from fiber conveying supports are disclosed including a doctor beam, a doctor blade having a web contacting edge, a hose for fluids for applying a force between the doctor beam and the doctor blade when pressurized to move the web contacting edge towards the fiber conveying support, the fiber web having a basis weight over 1000 g/m 2 , the doctor blade and doctor beam being pivotably attached, and the hose arranged for applying the force at a distance form the pivotable attachment to move the web contacting edge by pivoting the doctor blade relative to the doctor beam. | 3 |
CROSS REFERENCE TO RELATED APPLICATIONS
This application is a continuation-in-part of U.S. patent application Ser. No. 557,717, filed Mar. 12, 1975, now abandoned, which in turn is a continuation-in-part of U.S. patent application Ser. No. 418,524, filed Nov. 14, 1973, now abandoned. The latter is related to U.S. application Ser. No. 415,582, filed Nov. 14, 1973 by Robert M. Thompson and Richard S. Stearns, title of the application is "Copolymer of Blocks of Alternating Poly(dioxa-amide) and Polyamide". Also related are U.S. applications Ser. Nos. 415,583 and 415,610, both filed Nov. 14, 1973 by present inventor and titled "Block Copolymer of Poly(oxa-amide)and Polyamide" and "Block Copolymer of Poly(dioxa-arylamide) and Polyamide", respectively. Also related is U.S. application Ser. No. 415,581, filed Nov. 14, 1973 by Elmer J. Hollstein. Subject matter of the latter application relates to a method for the hydrogenation of a dinitrile which is a precursor of the hydrophilic polymer disclosed within the aforementioned related applications.
BACKGROUND OF THE INVENTION
It is known that commercially important polyamides, such as nylon-6, have excellent physical properties in many respects. However, for certain textile application fabrics and similar products prepared from such nylons are somewhat deficient in moisture absorption as compared to a natural fiber such as cotton. This characteristic is important because according to ENCYCLOPEDIA OF POLYMER SCIENCE AND TECHNOLOGY, Vol. 10, Section Polyamide Fibers, moisture absorption determines comfort factors, ease and cost of dyeing, antistatic character and hand or feel of the fabric. To overcome this moisture absorption deficiency many attempts have been made but none have been commercially successful to date.
Disclosed herein is a novel block copolymer which can be converted into a fiber having moisture absorption properties superior to that of commercially used polyamide such as nylon-6. This block copolymer consists of a specified polyamide and a specified poly(dioxa-amide). Surprisingly, the incorporation of a specified poly(dioxa-amide) into a specified polyamide does not adversely effect the many desirable fiber properties of the polyamide and, in fact, improvement in certain mechanical properties such as initial modulus and strength can be obtained. Furthermore, incorporation of said poly(dioxa-amide) materially improves its moisture absorption property. Also the copolymer can be formed into other desired shapes by extrusion, injection molding and other well-known thermoplastic forming methods.
A block copolymer can result when a mixture of polymer Z and polymer Y, both of which contain amides, is properly processed. Thus the resulting block copolymer contains relatively long chains of a particular chemical composition, the chains being separated by a polymer of different chemical composition; thus diagrammatically ##STR1## Another type of a block copolymer is one which contains relatively long chains of a particular chemical composition which are separated by a low molecular weight "coupling agent", thus diagrammatically ##STR2## Each of the aforementioned polymer chains, i.e., Z and/or Y, can be a homopolymer or a random copolymer.
Generally, copolymers containing an amide functional group, i.e., ##STR3## can be formed by melting two polyamides. Thus when two different polyamides are mixed and heated above their melting point copolymers are formed. This process is also known as melt blending. However, the length of time the polymers are maintained at a temperature above their melting points has a profound effect on the resulting structure. As the mixing at the elevated temperature begins the mass is a physical mixture of two different compounds. But gradually as the heating and mixing continues the mixture is converted into a copolymer characterized as a "block" copolymer. However, if the heating and mixing continues the length of the "blocks" decrease and sequences of "random" copolymers appear. If the heating and mixing occurs for a sufficient time most of the "blocks" disappear and mostly "random" sequences form as evidenced by deterioration of its physical properties including melting point. At present there is no known direct way of determining chain sequence of such a polymer. But indirect methods exist, such as melting points for example, and this is discussed in detail hereinafter. Controlled decomposition of such a copolymer will yield all identifiable components that make up the copolymer but will not indicate sequences.
Polymers, including copolymers, containing amide functional groups generally result from a reaction known as condensation. Condensation refers to a polymer-forming reaction in which water can be a by-product. The various types of polymers that can be produces from condensation (or step growth polymerization) are described hereinafter. The initial stage of a condensation polymerization consists of random combinations of two monomeric units to form dimer molecules. Examples of these could be the formation of two units of nylon-11 from the corresponding amino acid (11-aminoundecanoic acid) in the case of an AB polyamide ##STR4## or adipic acid molecule and hexamethylene diamine in an AABB system ##STR5## The letter "A" refers to one of the functional groups of the monomer, "B" refers to the other.
The foregoing dimer molecules will combine with equal facility with another monomeric unit or a dimer unit. In this fashion, the average degree of polymerization (DB) builds during the course of the reaction. This is discussed in greater detail in ORGANIC CHEMISTRY OF SYNTHETIC HIGH POLYMERS, Robert W. Lenz, Library of Congress Catalog Card No. 66-22057.
In the same manner, as reactions I and II, random copolymers can be formed. The only condition necessary is that more than one type (or two if an AABB system is used) of monomer unit be present during the condensation reaction. Thus following from the example above where monomer of AB and AABB polymers are present in the same reactor at the beginning of the polymerization, the AB monomer (amino acid) will react with a similar unit or the AABB monomer unit (the diamine or diacid) in a random fashion since their reactivities are similar. The final result of such a polymerization will be a random copolymer. If their reactivities are very dissimilar, there would be a tendency to become blocks, however, units having similar carboxylic and/or similar amine ends have similar reactivities. Further examples of random copolymers are given in U.S. Pat. No. 3,397,107 where the monomer units of N-303/T and caprolactam are polymerized in a random fashion. Another example is contained in U.S. Pat. No. 3,594,266 in which a polyethylene oxide diamine, terephthalic acid and caprolactam were polymerized in a random fashion. Since the condensation polymerization is a random sequence of events it would be extremely improbable to obtain an alternating copolymer using dissimilar monomer units in the condensation reaction as it is known today. An alternating copolymer can be classified as a special type of random copolymer.
Formation of a condensation block copolymer cannot be easily achieved using the conditions described heretofore because of the random reaction of monomeric units. Block copolymer preparations have been described in the patent literature using at least two techniques. One technique, as described before, is melt blending two homopolymers at temperatures where the polyamide becomes reactive to amide interchange, chain extension and hydrolysis. Such a technique is disclosed in U.S. Pat. No. 3,393,252. When the conditions are closely controlled block copolymers with a distribution of optimum sequence lengths can be prepared.
Another method of preparing block copolymers is described in U.S. Pat. No. 3,683,047. It consists of polymerizing two homoprepolymers of low molecular weight such as from 1000 to 4000. In this specific case, one prepolymer was carboxyl terminated while the other was amine terminated. The result of the polymerization is a block copolymer. Under the conditions of polymerization very little randomization occurred as indicated by little loss in melting point during the blend time. These block copolymers have been called ordered copolymers since by the nature of the starting materials reactive functional groups they cannot react with themselves.
Other examples of random copolymers are as follows. CHEMICAL ABSTRACT 88764f, Vol. 70, 1969, (Japanese Pat. No. 28,837/68) discloses a random copolymer having moisture retention properties prepared from the combination of (a) salt of bis(α-aminopropoxy)-ethane (also referred to as 30203) and adipic acid and (b) the monomer caprolactam. British Pat. No. 1,169,276 discloses a random copolymer having improved hydrophilic properties prepared from the combination of (a) salt (I) of H 2 N(CH 2 ) 3 --O--CH 2 --C(CH 3 ) 2 --CH 2 --O--(CH 2 ) 3 NH 2 and adipic acid and (b) the monomer caprolactam; also a random copolymer of the aforementioned salt (I) and hexamethylene diammonium adipate (H 3 + N(CH 2 ) 6 NHCO(CH 2 ) 4 COO) - ; also referred to as nylon-6,6 salt. CHEMICAL ABSTRACT 4514h, Vol. 49, 1955, discloses a random copolymer prepared from the (a) salt (II) of H 2 N(CH 2 ) 3 --O--(CH 2 ) 4 --O--(CH 2 ) 3 --NH 2 and adipic acid and (b) nylon-6,6 salt. Salt (II) upon heating forms a cream-colored material; such discoloration detracts from its utility where clarity is required. U.S. Pat. No. 3,522,329 discloses a random copolymer prepared from the (a) salt of diamine of polyethylene oxide (HOCH 2 CH 2 (O--CH 2 CH 2 ) n OH) and adipic acid and (b) ε-caprolactam (also called caprolactam). U.S. Pat. No. 3,514,498 discloses a random copolymer prepared from the (a) salt of diamine of polyethylene oxide and adipic acid and (b) ε-caprolactam.
Examples of block copolymers are as follows. The previously mentioned U.S. Pat. No. 3,514,498 also disclosed a block (random) copolymer prepared from two polymers; (a) polymer resulting from the salt of diamine of polyethylene oxide and adipic acid and ε-caprolactam and (b) poly-ε-capramide (nylon-6). U.S. Pat. No. 3,549,724 also discloses a block (random) copolymer prepared from (a) polymer prepared from polyethylene oxide diammonium adipate and ε-caprolactam and (b) nylon-6 or nylon-6,6. U.S. Pat. No. 3,160,677 discloses a block copolymer prepared from (a) a polymer prepared from dibutyloxalate [(COOC 4 H 9 ) 2 ] and a diamine and (b) polycaprolactam.
Because of the complexity in naming the copolymers of polyamide and poly(dioxa-amide), a shorthand nomenclature is used herein. It is based in part on the nomenclature used to identify aliphatic polyamides. Numbers signifies the number of carbon atoms in a polymer. The letter "O" signifies oxygen and its relative location within the polymer; "N" signifies polyamide linkage; "T" signifies terephthalic. Thus "30203" refers to a diamine function while "6" refers to the diacid function. Therefore, "6" refers to six carbon paraffinic diacid and in particular adipic acid. Also "30203" indicates the number of paraffinic carbons and the "O" indicates the placement of oxygen. In this nomenclature a slash (/) disignates a random copolymer whereas a double slash (//) indicates a block copolymer. Thus N-30203-6//6 indicates that blocks of N-30203-6 are connected within the copolymer with blocks of "6" (nylon-6).
Contrary to expectations based on the previously discussed art it has now been found that it is possible to prepare a composition comprising a block copolymer of polyamide and poly(dioxa-amide) having moisture uptake equivalent to that of cotton. In addition fibers of the copolymer have overall fiber properties substantially equivalent to that of such nylons as nylon-6.
SUMMARY OF THE INVENTION
Present invention resides in a novel composition. It has utility as a fiber as well as other utilities. The composition is a block copolymer of a specified polyamide and a specified poly(dioxa-amide). The polyamide portion of the molecule is a bivalent radical of a melt spinnable polyamide having no ether linkages. The poly(dioxa-amide) portion of this molecule contains both a double oxygen linkage, i.e., --R--O--R--O--R-- and amide linkage, i.e., ##STR6## The following repeating structural formula depicts the composition of this invention: ##STR7## wherein R 1 , R 2 and R 3 are selected from the group consisting of H, C 1 -C 10 alkyls and C 3 -C 10 isoalkyls; R 4 is selected from the group consisting of C 1 -C 10 alkylenes and C 3 -C 10 isoalkylenes; R 5 is selected from the group consisting of C 0 -C 10 alkylenes and C 3 -C 10 isoalkylenes; and y = 4-200 and z = 4-300. The molecular weight of the copolymer is about 5000-100,000.
DESCRIPTION
As stated heretofore one portion of the novel composition is a melt spinnable polymer having no ether linkages. Melt spinnable refers to a process wherein the polymer, a polyamide, is heated to above its melting temperature and while molten forced through a spinneret. The latter is a plate containing from one to many thousands of orifices, through which the molten polymer is forced under pressure. The molten polymer is a continuous filament and depending on the number of orifices many filaments can be formed at the same time. The molten filaments are cooled, solidified, converged and finally collected on a bobbin. This technique is described in greater detail in ENCYCLOPEDIA OF POLYMER SCIENCE AND TECHNOLOGY, Vol. 8, Man-Made Fibers, Manufacture.
If a single fiber is extruded, as in the case when it is intended to be knitted into hosiery, the product is called a monofilament. When the product is expected to be converted into a fabric by knitting or weaving, the number of monofilaments is in the range of 10-100. Such a product is known as a multifilament yarn. Yarns for industrial application, such as in the construction of tire cords, usually contain several hundred to a thousand or more filaments. When the fibers are used to make a spun yarn, i.e., a yarn formed by twisting short lengths of fibers together, as is the practice with cotton, the number of orifices can rise to tens of thousands. The extruded material is cut into pieces in the range of 1-5 inches long to produce "staple" fiber. This stable fiber is converted into spun yarn in the same manner as cotton. Polymer of present invention can be prepared into the aforementioned forms by the various methods disclosed.
Also, the polymers of present invention can be used to prepare nonwovens. Nonwoven refers to a material used as a fabric made without weaving, and in particular having textile fibers bonded or laminated together by adhesive resin, rubber or plastic or felted together under pressure. Many such methods are described in detail in MANUAL OF NONWOVENS, Prof. Depl-Ing and Dr. Radko Krema, Textile Trade Press, Manchester, England.
Polyamides which are crystallizable and have at least a 30° C. difference between melting point and the temperature at which the molten polymer undergoes decomposition can be melt spun. Examples of melt spinnable polyamides having no ether linkages are as follows: nylon-6,10 [poly(hexamethylene sebacamide)]; nylon-6 [poly-(pentamethylene carbonamide)]; nylon-6,6 (hexamethylene adipamide); nylon-11 [poly(decamethylene carbonamide)]; MXD-6 [poly(meta-xylene adipamide)]; PACM-9 [bis(para-aminocyclohexyl)-methane azelamide]; PACM-10 [bis(para-aminocyclohexyl)methane sebacamide]; and PACM-12 [bis(para-aminocyclohexyl)methane dodecanoamide]. Others are listed in ENCYCLOPEDIA OF POLYMER SCIENCE AND TECHNOLOGY, Vol. 10, Section Polyamide Fibers, table 12. Methods for preparing these polyamides are well known and described in numerous patents and trade journals.
The poly(dioxa-amide) portion of the composition can be prepared by the following generalized scheme: ##STR8##
Reaction (1) is often referred to as cyanoethylation; particularly wherein R 1 , R 2 and R 3 = H; also these R's can be C 1 -C 10 alkyls or C 3 -C 10 isoalkyls. R 4 can be one of the following: C 1 -C 10 alkylene and C 3 -C 10 isoalkylene. Reaction (2) is a hydrogenation. Reaction (3) is the reaction between a diacid and diamine resulting in a salt. R 5 can be one of the following: C 0 -C 10 alkylene and C 3 -C 10 isoalkylene. Reaction (4) is often referred to as a condensation polymerization. Here the repeating unit contains fewer atoms than the monomer, and necessarily, the molecular weight of the polymer as formed is less than the sum of the molecular weights of all the original monomer units which were combined in the reaction to form the polymer chain. Examples of C 1 -C 10 alkyls are methyl, propyl, butyl, pentyl, etc.; examples of the C 3 -C 10 isoalkyls are isopropyl, isobutyl, isopentyl and the like. Examples of C 1 -C 10 alkylenes are as follows: methylene, dimethylene, trimethylene and the like; examples of C 3 -C 10 isoalkylenes are as follows: methyltrimethylene, 2-methyltetramethylene and the like.
A variation of preparation reactions (1) and (2) is also disclosed in CHEMICAL ABSTRACT 3935K, Vol. 71 (1969) S. African Pat. No. 6,704,646.
Examples of HOR 4 OH of reaction (1) are as follows: ethylene glycol, propylene glycol and trimethylene glycol. Examples of HOOCR 5 COOH of reaction (3) are as follows: oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, undecanedioic, α,α-diethylsuccinic and α-methyl-α-ethyl suberic.
Examples of poly(dioxa-amide) polymer that can be prepared in the aforementioned generalized scheme are the following: ##STR9##
The aforementioned blocks of poly(dioxa-amide) and melt spinnable polyamide having no ether linkages can contain as few as four repeating units within the polymer of present invention. Thus the aforementioned y and z both can equal 4. Data reported in the Examples show that a melt spinnable polyamide, as an illustration, having four repeating units has an estimated melting point which does not differ substantially from the melting point of its relatively high molecular weight polymer. Similar data, also reported in the Examples, for a poly(dioxa-amide), shows that 30203-6 having four repeating units has a melting point which does not differ substantially from the melting point of its relatively high molecular weight polymer. Thus each four repeating unit block, when present in a block copolymer, can retain its own particular properties without substantially degrading the properties of the other repeating unit block. To minimize loss of properties the preferred minimum values for y and z are eight and more preferred values are ten. Preferred maximum values of y and z are about 175 and 185, respectively, more preferred values are about 100 and 130 but values of 200 and 300 are operative. Values of y and z are median values.
The polymers of present invention can also contain an antioxidant such as 1,3,5-trimethyl-2,4,6-tris-(3,5-ditertiary-butyl-4-hydroxybenzyl)benzene. Small amounts of antioxidant, e.g., 0.5 weight percent, are satisfactory, however, as little as 0.01 weight percent can be used or as much as 2.0 weight percent also can be satisfactory. Antioxidants other than the aforementioned one can be used. The antioxidant generally would be mixed in combination with the two polymers prior to melt blending. Other usual additives for polyamides such as delusterants and/or light stabilizers can also be incorporated.
EXAMPLES
The following describes how the various novel polymers and their precursors were prepared, and the influence of certain variables upon their properties. Also reported are results on comparative polymers.
1. Preparation of 1,2-bis(β-cyanoethoxyethane) [NC--(CH 2 ) 2 O--(CH 2 ) 2 --O--(CH 2 ) 2 --CN]
To a 5 liter double walled (for water cooling) glass reactor with a bottom drain and stopcock was charged 930 grams (15 moles) of ethylene glycol and 45.6 grams of 40% aqueous KOH solution. Some 1620 grams (30.6 moles) of acrylonitrile (NC--CH═CH 2 ) were then added dropwise with stirring at such a rate that the temperature was kept below 35° C. After the addition was completed the mixture was stirred an additional hour and then allowed to stand overnight. The mixture was then neutralized to a pH of 7 by the addition of 6 molar HCl. After washing with saturated NaCl solution three times, the product was separated from the aqueous layer, dried over CaCl 2 and passed through an Al 2 O 3 column to insure that all basic materials had been removed. The yield obtained was 90% of theoretical.
2. Preparation of 4,7-dioxadecamethylenediamine [NH 2 (CH 2 ) 3 --O--(CH 2 ) 2 --O--(CH 2 ) 3 --NH 2 ]
In an 800 milliliter hydrogenation reactor was charged 150 grams of 1,2-bis(β-cyanoethoxyethane), 230 milliliters of dioxane and about 50 grams Raney Co. After purging the air, the reactor was pressurized with hydrogen up to 2000 psi and heated to 110° C. As the hydrogen was consumed additional hydrogen was added until pressure remained constant. Upon cooling, the pressure was released and the catalyst was filtered. The dioxane was removed by atmospheric distillation. The remaining mixture was distilled by a 3 foot spinning band distillation unit. The diamine distilled at 123°-214° C. and 3.75 mm Hg. About 98 grams of 99.95% pure material were obtained. The material can be referred to as 30203 diamine.
3. Preparation and Polymerization of Poly(4,7-dioxadecamethylene adipamide) (N-30203-6)
To a solution of 41.50 grams of adipic acid dissolved in a mixture of 250 milliliters of isopropanol and 50 milliliters of ethanol was added, with stirring, 50 grams of the 30203 diamine dissolved in 200 milliliters of isopropanol. An exothermic reaction occurred. Upon cooling, a polymer salt crystallized out of solution. The salt was collected on a Buchner funnel and subsequently recrystallized from a mixture of 400 milliliters of ethanol and 300 milliliters of isopropanol solution. The product, dried in vacuo overnight at 60° C., had a melting point of 128° C. and the pH of a 1% solution was 6.9. 85 Grams (92% yield of theoretical) of the salt was obtained.
About 40 grams of the polymer salt were charged to a heavy walled glass polymer "D" tube. Then the neck of the tube was constricted for sealing and purged of air by evacuating and filling with nitrogen five times. Finally the tube was heated in an aluminum block for 2 hours at 200° C. After cooling the tip of the tube was broken off and the remaining portion was bent over at a 45° angle by heating and then connected to a manifold and purged of air with nitrogen vacuum cycles. The tubes were heated at 222° C. under nitrogen at atmospheric pressure for 6 hours using methyl salicylate vapor baths. On cooling, the tubes were broken and the polymer plug cut to 1/8 inch size pieces. The resulting polymers had inherent viscosities ranging from 0.9 to 1.1 in a meta-cresol solution.
4. Polymer Melt Blending
Suitable amounts of dried N-30203-6 and nylon-6 were charged to a large test tube having two openings in the rubber stopper. The openings were for a helical stirrer and a nitrogen inlet. The container was purged of air. Afterwards the nitrogen-filled container was heated using a suitable liquid-vapor bath. The mixture of the two polymers was agitated with the helical stirrer powered by an air motor for the required time. Before allowing the molten polymer to cool the stirrer was lifted to drain the polymer. After solidification the material was broken up and dried for spinning.
5. Polymer Spinning and Drawing
After the aforementioned melt blending the polymer was charged to a micro spinning apparatus consisting of stainless steel tube (5/8 inch OD × 12 inch) with a 0.037 inch capillary. The tube was heated with a vapor bath to the temperature consistent with the polymer. Generally about 245° C. was used. Nitrogen was swept through the polymer until the polymer melted and sealed the capillary. After the polymer was completely melted and a uniform temperature had been reached (about 30 minutes) the nitrogen pressure was increased by about 30-50 psig (depending on the polymer melt viscosity) to extrude the polymer.
Due to the nature of this apparatus, it could not be equipped with a filter system to remove particles from polymer melt. This made spinning polymers that were prone to form gel particles such as nylon-6,6 difficult to spin continuously.
The fiber as it left the tube was drawn on a series of rollers and wound up on a bobbin. The first roller or feed roll was traveling at 35 ft/min. The filament was wrapped five times around this. After crossing a hot pipe maintained at about 50° C. the filament was wrapped around the second roller or a draw roll (five times) which speed varied depending on the draw ratio required (130-175 ft/min). Unlike commercial draw rolls, the fiber tended to abrade itself; that is the fiber coming off rubbed against fiber coming on. This made higher draw ratios difficult to obtain. The third roll had a removable bobbin and was driven at a slightly lower speed than the draw roller.
Draw ratio refers to the ratio of the speed of the second roller or draw roll to the speed of the first roller or feed roll. Thus if the second roller was traveling at 175 ft/min and the first roller at 35 ft/min the draw ratio is five (175/35). This difference in speeds of the rollers stretches the fiber. Stretching or drawing orientates the molecules, i.e., places them in a single plane running in the same direction as the fiber.
6. Results of Tests and Comparative Runs
The accompanying Table I shows the effect of melt blending's temperature and time on various properties of block copolymers having different proportions of poly(dioxa-amide) and polyamide. Also shown are comparative results.
Comparision of Runs 1, 3 and 5 indicate that at relatively low temperatures and short blending time the addition of substantial amounts of N-30203-6 into nylon-6 does not substantially lower the melting point of the resulting N-30203-6//6. Decreases in tenacity and initial modules are noted while an increase in elongation exists.
Comparison of Runs 5, 6 and 7 indicates that as the blending time at a constant temperature increases a decrease in melting point occurs. This indicates a decrease in the amount and size of "blocks" and further indicates an increase in the amount of "randomness".
Indirectly it is known that crystallinity of a block copolymer falls off as the alternating sequences increase. Thus properties dependent on crystallinity such as melting point and tenacity decrease as alternating increases.
The fact that inherent viscosity, a measurement indicating molecular weight, increases means that the molecular weight is increasing thereby eliminating degradation as a reason for the change in melting point. The increase in blending time also causes a reduction in tenacity, elongation and initial modulus.
Comparison of Runs 7, 8 and 9 indicates that while maintaining a constant blending time, as the temperature of blending increases, decreases occur in inherent viscosity and melting point. Also decreases in tenacity and initial modulus occur.
Tenacity, elongation (elongation to rupture) and initial modulus (textile modulus) and the methods for obtaining such values are defined and described in Kirk-Othmer, ENCYCLOPEDIA OF CHEMICAL TECHNOLOGY, 2nd ed., Vol. 20, Textile Testing.
Accompanying Table II shows the moisture regain of several block copolymers having different proportions of poly(dioxa-amide) and polyamide. Also shown are comparative results for nylon-6 and cotton.
Comparison of Runs 1-6 (Table II) demonstrates that increasing the amount of poly(dioxa-amide) in the block copolymer increases moisture regain substantially compared to the moisture regain of nylon-6 at various relative humidities. Also comparison of Runs 7 and 6 indicates that said block copolymer containing 30% N-30203-6 has a moisture regain better than cotton at 95% and 85% relative humidities and almost equal at lower levels of 65% and 75% relative humidities.
Moisture regain refers to the amount of moisture a dried sample of fiber picks up in a constant relative humidity atmosphere. Measurement of this property was carried out using a series of humidity chambers made from dessicators containing suitable saturated salt solutions (i.e., NaNO 2 = 65%; NaCl = 75%, KCl = 85% and N 2 SO 3 = 95%) at room temperature.
To determine moisture regain first a sample of the fiber was dried in a vacuum dessicator over P 2 O 5 . After a constant weight was obtained the sample was placed in one of the appropriate chambers. The chamber was then evacuated to speed up equilibrium. The fiber remained in the chamber until a constant weight was obtained. The increase in weight of the sample over the dried sample was the amount of moisture regained.
Accompanying Table III shows the effect of boil off on moisture regain of several block copolymers prepared at different blending temperatures and times. Also shown are weight losses which occurred during boill off. Comparative data for nylon-6 is also reported.
Boil off refers to the placement of the fiber in boiling water for a specified length of time. Afterwards the weight loss was determined. Also after following the procedure described for determining moisture regain the incremental increase in percent moisture regain at 65% relative humidity was determined. Boil off can be considered as akin to a dye treatment.
The increase in moisture regain as a result of boil off is thought to best be understood by the following explanation. By placing the fiber in boiling water portions of the fiber relax. Thus the orientated amorphous sections tend to open up. Boiling off speeds up the relaxation of this unnatural state. This opening up permits the fiber to take up more moisture that it otherwise would be capable of. Heating the fiber, by other than placing in boiling water, will also relax the fiber. Weight loss comparisons of Runs 3, 2 and 1 indicate again that as blending time is increased the polymer becomes more random.
Accompanying Table IV demonstrates the effect of various draw ratios in moisture regain, tenacity, elongation and initial modulus of several block copolymers of poly(dioxa-amide) and polyamide.
The data indicates that as draw ratios were increased generally moisture regain decreased except at a 95% relative humidity. Also as the draw ratios were increased tenacity and initial modulus increased but elongation decreased.
Accompanying Table V shows the effect of percent of N-30203-6 in 30203-6//6 on dye uptake. The data indicates that as the percent of N-30203-6 in N-30203-6//6 increase dye uptake increases. Compared to water molecules, dyes are larger molecules and cannot penetrate the crystalline structure of nylon fiber, thus dye uptake can be related to the amount of amorphous regions in the fiber.
The amount of dye uptake was measured in the following manner. The preweighed fibers were dyed in suitable containers at room temperature. The concentration of the "direct" yellow 28" in the aqueous dye solution was measured before and after spectrophotometrically. The dyeing was considered complete when no decrease in dye concentration was observed over several hours. Prior to dyeing it was determined that the initial concentration of the dye in the bath had to be greater than 5.8 × 10 -5 grams per milliliter so that the measured dye absorption was independent on the initial dye concentration.
Accompanying Table VI describes the relative oxidation degradation of a block copolymer of poly(dioxa-amide) and polyamide. The data indicates that the copolymer N-30203-6//6 suffers tenacity losses when exposed to air at elevated temperatures; comparison of Runs 4, 5 and 6. However, the data also indicates that a small amount of antioxidant, e.g., 1,3,5-trimethyl-2,4,6-tris-(3,5-ditertiary-butyl-4-hydroxybenzyl)benzene, at least prevents tenacity losses and perhaps even increased tenacity; comparison of Runs 8 and 5, 9 and 6. Also shown is the relative stability of nylon-6; the increase in tenacity of nylon-6 in comparative Run 2 is believed to be the result of annealing.
Surprisingly in Run 5, although a tenacity loss was sustained, virtually no discoloration occurred.
In Runs 7, 8 and 9 the aforementioned antioxidant was added in the amount of 0.5 weight percent prior to melt blending.
The data of Table VI was obtained in the following manner. The fibers listed in the table were placed in a forced air oven maintained at 120° C. for the listed times. After sufficient time had passed, samples were removed and tested for changes in tenacity.
7. Minimum Value for Repeating Units
To determine how few repeating units, i.e., y and z, could be contained within a block and still retain its polymeric properties the data shown in the accompanying Tables VII and VIII were obtained. To obtain the data five samples of nylon 30203-6 salt were polymerized at various conditions as shown in Table VII and subsequently average molecular weights and melting points were determined. These results are reported in Table VII. Dividing the measured average molecular weight by the molecular weight of the repeat unit in the polymer, which is 286, the average value of y is computed. This value is also reported in Table VII. Also shown is the melting point of the N-30203-6 salt monomer. Also, three samples of caprolactam were polymerized at various conditions as shown in Table VIII and subsequently average molecular weights and melting points were determined. The foregoing two tests were also run on one sample of a purchased polymer. Average values of z were calculated in a similar manner as y. Also shown is the melting point of the caprolactam monomer. Also shown in Table VIII is an estimated value for z. This estimtaed value is based on an extrapolation of Runs 1-3 via semi-log graph paper.
For both of the foregoing blocks the relatively small decrease in melting point compared to the substantial decrease in number of repeat units, i.e., y and z, indicates that four repeating units can be contained in a block without adversely changing the properties of the block.
8. Others
Analogous results are obtained when nylon-6,10; nylon-11; MXD-6; PACM-12 and others are used in place of nylon-6 in the polymer melt blending step (4). Also, analogous results are obtained when in step (3), adipic acid is replaced with one of the following acids: oxalic, malonic, succinic, glutaric, pimelic, suberic, azelaic, sebacic, undecanedioic, α,β-diethylsuccinic and α-methyl-α-ethylsuberic. When the ethylene glycol of step (1) is replaced with one of the following glycols: trimethylene, propylene and tetramethylene analogous results are obtained.
9. Comparative Data
Accompanying Table IX compares moisture retention of applicant's N-30203-6//6 with N-30203-6, N-30203-6/6 and a composite fiber of N-30203-6/6 and nylon 6. The moisture retention procedure is described in a footnote in the Table.
Comparison of fibers of block copolymers 7 and 8 with the other fibers indicates their superiority as to moisture retention.
TABLE I__________________________________________________________________________EFFECT OF MELT BLENDING ON PROPERTIES OF BLOCK COPOLYMEROF POLY (DIOXA-AMIDE) POLYAMIDE (N-30203-6//6 Percent Blending Inherent Melting of Temp. Viscos- Point Tenac- Elonga- Initial.sup.(b)Run Polymer 30203-6 ° C Minutes ity.sup.(c) ° C.sup.(c) ity.sup.(b) * tion %.sup.(b) Modulus*__________________________________________________________________________1 nylon-6 0 NA NA 1.10 219 3.7 45 11.52 N-30203-6 100 NA NA 0.89 182 -- -- --3 N-30203-6//6 10 282 15 1.15 219 2.6 43 12.04 " 10 282 180 1.18 215 3.5 60 12.05 " 20 282 15 1.03 218 2.9 68 9.06 " 20 282 180 1.04 213 3.0 66 8.07 " 20 282 360 1.10 205 2.3 59 7.08 " 20 295 360 0.73 195 1.9 59 7.09 " 20 305 360 0.68 193 1.4 64 5.510 " 25 295 30 1.05 214 2.2 64 6.311 " 30 295 30 1.03 220.sup.(a) 2.1 65 7.2__________________________________________________________________________ .sup.(a) Believed not to be representative sample. .sup.(b) Draw ratio 3.7 ambient RH, but no significant differences observed at various RH; 40 monofilaments twisted together average of 7 or 8 samples per test. .sup.(c) Fiber *Units are grams/denier. NA = Not Applicable
TABLE II__________________________________________________________________________MOISTURE REGAIN OF BLOCK COPOLYMER OF POLYAMIDE ANDPOLY(DIOXA AMIDE) (N-30203-6//6, MONOFILAMENT, AFTER BOIL OFF) Percent of 30203-6 in Moisture RegainRun Material Material 95% RH.sup.(b) 85% RH.sup.(b) 75% RH.sup.(b) 65% RH.sup.(b)__________________________________________________________________________1 nylon-6 0 7.6 5.8 4.5 4.12 N-30203-6//6.sup.(a) 10 10.0 7.4 5.9 4.53 " 15 11.7 8.2 6.3 4.44 " 20 12.2 9.2 7.2 5.25 " 25 13.0 10.0 7.3 5.46 " 30 15.5 12.1 8.6 6.07 cotton 0 14.5 11.8 9.5 7.6__________________________________________________________________________ .sup.(a) Melt blended at 295° C for 30 minutes, draw ratio 3.7 .sup.(b) % RH = percent relative humidity.
TABLE III__________________________________________________________________________EFFECT OF BOIL OFF ON MOISTURE REGAIN OF BLOCKCOPOLYMER OF POLY(DIOXA-AMIDE) AND POLYAMIDE Incremental Increase in Percent of Blending Conditions Weight % Moisture 30203-6 in Temp, Time, Loss.sup.(a) Regain atRun Material Material ° C Minutes % 65% RH__________________________________________________________________________1 nylon-6 NA NA NA 1.4 0.52 N-30203-6//6 20 282 360 1.8 0.73 " 20 282 15 3.9 --4 " 20 295 60 3.3 --5 " 20 295 30 3.4 --6 " 20 295 15 3.4 --7 " 25 295 60 -- 1.8__________________________________________________________________________ ##STR10## NA = not applicable
TABLE IV__________________________________________________________________________EFFECT ON DRAW RATIO ON PROPERTIES OF BLOCK COPOLYMER OFPOLY(DIOXA-AMIDE) POLYAMIDE (N-30203-6//6)% 30203-6 Elonga-in N-30203 Draw Moisture Regain.sup.(c) Tenac- tion % InitialRun -6//6.sup.(e) Ratio.sup.(a) 95% RH 85% RH 75% RH 65% RH.sup.(b) ity.sup.(d) * .sup.(d) Modulus.sup.(d) *__________________________________________________________________________1 25 3.7 13.0 10.0 7.3 5.4 2.2 64 6.32 25 4.5 14.2 10.1 7.4 5.2 2.8 40 13.03 25 5.0 -- -- -- -- 2.9 24 15.04 30 3.7 15.5 11.7 9.6 6.0 2.1 65 7.25 30 4.5 14.0 11.8 7.8 5.7 2.8 59 8.66 30 5.0 -- -- -- -- 3.7 52 16.2__________________________________________________________________________ .sup.(a) Ratio of speed of second roller to speed of first roller. .sup.(b) % RH = percent relative humidity. .sup.(c) Monofilament .sup.(d) 40 monofilaments twisted together; average of 7 or 8 samples per test. .sup. (e) Blending is 295° C and 30 minutes. *Units are grams/denier.
TABLE V______________________________________EFFECT OF PERCENT OF POLY(DIOXA AMIDE) INBLOCK COPOLYMER ON DYE UPTAKE.sup.(a)Percent of 30203-6 Dye AbsorptionRun in N-30203-6//6.sup.(b) moles/gram of fiber × 10.sup.2______________________________________1 0 1.002 10 1.653 15 1.904 20 2.155 30 2.70______________________________________ .sup.(a) Direct Yellow 28, 6 × 10.sup.-5 grams/milliliter. .sup.(b) Melt blending 30 minutes at 295° C, draw ratio 3.7.
TABLE VI______________________________________RELATIVE OXIDATION DEGRADATION OF BLOCKCOPOLYMER OF POLY(DIOXA-AMIDE) ANDPOLYAMIDE (N-30203-6//6-TWISTED FILAMENTS) Percent of OriginalRun Material.sup.(d) Time at 120° C.sup.(e) Tenacity Retained.sup.(a)______________________________________1 nylon-6 0 --2 nylon-6 1 1083 nylon-6 2 984 N-30203-6//6.sup.(b) 0 --5 N-30203-6//6.sup.(b) 1 876 N-30203-6//6.sup.(b) 2 707 antioxidant.sup.(c) &N-30203-6//6.sup.(b) 0 --8 " 1 1019 " 2 108______________________________________ .sup.(a) Untreated material has base tenacity of 100; thus a value >100 means an increase; <100 means a decrease. .sup.(b) Ratio of 30203-6 to 6 is 30/70. .sup.(c) 0.5% ethyl antioxidant 330 added prior to melt blending. .sup.(d) Melt blending 30 minutes at 295° C; draw ratio 3.7. .sup.(e) Hours.
TABLE VII______________________________________MOLECULAR WEIGHTOF N-30203-6 VS. ITS MELTING POINT Resultant Polymer (30203-6 Salt) Average Value Melting Molecular of PointRun Conditions Weight.sup.(a) y.sup.(b) ° C.sup.(c)______________________________________1 9.5 hrs at 208-232° C & 25,000 87 167250 psi, then 3 hrs at232° C and atm. press.2 9.5 hrs at 208-232° C, 12,987 45 167250 psi3 40 minutes at 240° C 3,247 11.4 1614 90 minutes at 190° C 2,088 7.3 1595 50 minutes at 190° C 1,091 3.8 1586 30203-6 salt monomer 286 (+18 1 125.sup.(d) for H.sub.2 O)______________________________________ .sup.(a) Molecular weight is based on amino ends. .sup.(b) Average molecular weight divided by 286 which is molecular weigh of 30203-6 repeat unit. .sup.(c) Melting point determined by Differential Scanning Colorimeter; onset value. .sup.(d) Relatively high melting point is caused by high degree of association caused by positive and negative charges contained within the salt.
TABLE VIII______________________________________MOLECULAR WEIGHTOF NYLON-6 VS. ITS MELTING POINT Resultant Polymer (Caprolactam) Average Value Melting Molecular of PointRun Conditions Weight.sup.(a) z.sup.(b) ° C.sup.(c)______________________________________1 Purchased 23,809 211 2092 3 hrs at 250° C and 7,874 70 2051 ml H.sub.2 O3 3 hrs at 250° C and 6,211 55 2014 ml H.sub.2 O4 2 hrs at 250° C 2,024 18 1885 monomer (caprolactam) 113 1 70______________________________________ .sup.(a) Molecular weight is based on amino ends. .sup.(b) Average molecular weight divided by 113 which is molecular weigh of nylon's monomer, i.e., caprolactam. .sup.(c) Melting point determined by Differential Scanning Colorimeter; onset value.
TABLE IX__________________________________________________________________________COMPARISON OF FIBERS CONSISTING OF VARIOUS POLYMERSFiber % of N-30203-6ProductMonocomponent Composition in Overall Moisture Retention.sup.(c)No. or Bicomponent of Fiber Composition 6500 rpm.sup.(d) 8400 rpm.sup.(d)__________________________________________________________________________1 mono N-30203-6 NA Degrades during test.sup.(e)2 mono Nylon-6 NA 12, 11.3 10, 10.43 bi N-30203-6/6.sup.(a) 5 16 134 bi N-30203-6/6.sup.(a) 20 Degrades during test.sup.(e)5 bi N-30203-6/6.sup.(a) 25 Degrades during test.sup.(e)6 bi N-30203-6/6.sup.(a) 30 Degrades during test.sup.(e)7 mono N-30203-6//6.sup.(b) 30 27.8 27.18 mono N-30203-6//6.sup.(b) 30 28 28.1__________________________________________________________________________ .sup.(a) Fiber is side by side bicomponent, i.e., .sup.x Z.sub.φ -Z.sub.y ; wherein N-30203-6 is X and nylon-6 is Y. Also N-30203-6/6 is random copolymer. .sup.(b) Applicant's fiber is block copolymer; each composition was forme at different blend conditions, product No. 9 at 283° C for 30 minutes; product No. 10 at 283° C for 45 minutes. .sup.(c) L.A. Welow, H.M.I. Zufle, A.U. McDonald, Textile Research Journal, Vol. 22, page 261, 1952. Moisture retention is determined by placing sample in boiling water for 5 minutes, then removing and placing in room temperature water and allowing it to stand overnight. Removed fro the water and centrifuged at 6500 rpm or 8400 rpm for 20 minutes to remov surface water; then weighed and dried overnight at 80° C and then reweighed. The difference in weight is amount of water retained. .sup.(d) Speeds used in the centrifuge to remove surface water. .sup.(e) Degrading means that fiber dissolves or plasticizes in water to form a melt or the fiber becomes very tacky. | Novel block copolymer formed by melt blending a melt spinnable polyamide such as nylon-6 and a poly(dioxa-amide) such as poly(4,7-dioxadecamethylene adipamide) which is also known as N-30203-6 is disclosed. Said copolymer has utility as a fiber. The fiber of disclosed copolymer, for example, of nylon-6 and said poly(dioxa-amide) has moisture absorption characteristics similar to that of cotton. Resulting copolymer is also known as N-30203-6//6. Furthermore, the resulting fiber still maintains the other desirable properties of the major constituent, for example, nylon-6. | 2 |
FIELD OF THE INVENTION
This invention relates to gene expression, and to the regulation of gene expression, in plants. In particular, the invention relates to DNA promoter sequences, and to expression cassettes containing the sequences, which can be introduced into plants for purposes of regulating transcription of associated coding sequences. In addition, the invention relates to expression vectors which contain such expression cassettes and which are of use in transforming plants.
BACKGROUND OF THE INVENTION
A promoter is a sequence of DNA which can affect or control the level of transcription and which is responsible for (or provides the site for) the binding of RNA polymerase. The position of a promoter is fixed relative to the transcription start site within the genome of an organism. RNA polymerase is an enzyme (or a class of enzymes) which can bind to a promoter and bring about transcription of the structural gene (coding region) that is under control of the promoter, resulting in the production of messenger RNA (mRNA). Messenger RNA in turn provides the template for synthesis of polypeptides (translation).
Promoters have been studied in a variety of organisms, including viruses (e.g., U.S. Pat. Nos. 4,495,280, 4,518,690); bacteria (e.g., U.S. 4,551,433); plants; and animals. For a given species or type of organism, conserved regions of DNA (consensus sequences) have been found within promoters associated with a variety of structural genes. These regions are believed to be involved in the role played by the promoter in the transcription process.
Initiation of the transcription process in plants involves the interaction of a promoter with RNA polymerase II. Consensus sequences within plant promoters have been found at positions upstream from the 5' end of the transcription start point. There is a sequence of about seven base pairs positioned approximately 19-27 base pairs upstream of the transcription start point (i.e., positions -19 to -27) which is known as the TATA sequence, believed to play a role in RNA polymerase entry. There is another sequence of about nine base pairs positioned approximately 70 to 80 base pairs upstream from the transcription start point which is known as the CAAT box, believed to be involved in the regulation of the level of transcription. Other regions upstream of the transcription start point have been identified which affect the frequency of initiation of transcription in eukaryotes. These DNA sequences, known as enhancers or viral enhancer elements, have been found to affect the activity of promoters in their vicinity; these sequences are not promoters, as defined herein, in that their position need not be fixed. See H. Weiher et al., Science, 219, 626-631 (1983).
There have been studies of the introduction into plants of bacterial genes fused to bacterial promoters, resulting in expression of the bacterial gene in the plant. These introductions have involved the insertion of foreign DNA into the Ti plasmid of Agrobacterium tumefaciens, and the introduction of the foreign DNA into plants using Agrobacterium containing the modified Ti plasmid. See, e.g., R. T. Fraley et al., Proc. Natl. Acad. Sci., 80, 4803-4807 (1983).
In order to provide high levels of expression of foreign genes in plant cells it is desirable to isolate the promoter regions from strongly expressed plant genes and use these fused with the foreign gene coding sequence to direct high levels of expression. Certain polypeptides known to be highly expressed in plants have been the subject of considerable study. One of these is the small subunit of the enzyme ribulose-1,5-bisphosphate carboxylase (RuBPCase). RuBPCase is the primary enzyme of the carbon fixation pathway in chloroplasts of plants of the C3 class. The enzyme consists of two types of polypeptide subunits, the small subunit (SSU) and the large subunit (LSU), eight of each of which assemble to give one molecule of RuBPCase. The small subunit, molecular weight approximately 14,000, is nuclear encoded and synthesized in the cytoplasm as a higher molecular weight precursor which includes a portion called the transit peptide. The precursor is transported into the chloroplasts via the mediation of the transit peptide. The precursor is processed to the mature subunit by post-translational mechanisms. The large subunit, molecular weight approximately 55,000, is encoded by chloroplast DNA and synthesized inside the chloroplast. The small subunit and large subunit are assembled in the chloroplast to yield RuBPCase.
RuBPCase is known to accumulate in response to light and studies have shown that there is a corresponding increase in the steady state levels of SSU mRNA resulting from increased transcription of the SSU gene. S. M. Smith et al., J. Mol. Appl. Genet., 1, 127-137 (1981) Studies have also shown that there are multiple copies of the SSU gene in the nuclear DNA of various plant genomes, including petunia (P. Dunsmuir et al., Nucleic Acids Res., 11, 4177-4183, 1983); pea (A. Cashmore et al., Genetic Engineering of Plants, T. Kosuge ed., 29-38, 1983); wheat (S. L. Berry-Lowe et al., J. Mol. Appl. Genet., 1, 483-498, 1982); and Lemna (C. F. Wimpee et al., Plant Molecular Biology, R. B. Goldberg ed., 12, 391-401, 1983).
In early work on the isolation of a cloned cDNA for the SSU gene in pea, there was a report of the sequence of a clone p20 corresponding to 123 amino acids of mature SSU, 13 amino acids of transit peptide, and 260 nucleotides of 3' non-coding region. J. Bedbrook et al., Nature, 287, 692-697 (1980). Subsequently, there were reports of sequence information for another pea cDNA clone, pSS15, and the corresponding genomic fragment pPS-2.4. G. Coruzzi et al., J. Biol. Chem., 258, 1399-1402 (1983); G. Coruzzi et al., EMBO J.,3 1671-1679 (1984). The isolation and characterization of petunia cDNA clones pSSU41, pSSU51, pSSU71, and pSSU117 and sequence information corresponding to part of the mature peptide region plus the 3' untranslated region for cDNA clones pSSU51 and pSSU117, was reported in P. Dunsmuir et al., Nucleic Acids Res., 11 4177-4183 (1983).
There have been reports of reintroductions into tobacco cells of promoter regions derived from pea SSU genes fused to bacterial gene coding regions. The introduction into tobacco, and expression, of a chimaeric gene consisting of the 5' region (promoter) of pea SSU gene labelled SS3.6 plus the coding region of the bacterial chloramphenicol acetyltransferase (CAT) and the 3' region of nopaline synthetase (nos) was reported in L. Herrera-Estrella et al., Nature, 310, 115-120 (1984). In this report the 5' region was fused to the coding region at a position 4 nucleotides upstream from the transcription initiation site. Another report disclosed the fusion of promoter and transit peptide DNA (plus the first codon--methionine--of the mature peptide region) from pea SSU gene SS3.6 to the structural gene for the bacterial protein neomycin phosphotransferase II, the introduction of the fused gene into tobacco plants, and the transport of the structural gene to the chloroplast in transformed plants. G. van den Broeck et al., Nature, 333, 358-363 (1985). A similar disclosure appears in P. H. Schreier et al., EMBO J., 4, 25-32 (1985), except that the promoter-transit peptide component contained additional DNA including the first 22 codons of the SSU mature peptide. There has also been a report of the introduction of DNA for pea SSU gene labelled pS4.0 into petunia, under the control of its own promoter, to yield heterologous RuBPCase containing pea SSU and petunia LSU. R. Broglie et al., Science, 224, 838-843 (1984).
SUMMARY OF THE INVENTION
In accordance with the invention, a new promoter system is provided which may be used to express foreign structural genes in plants (the word "foreign" meaning that the structural gene does not naturally occur in association with the promoter in question). The invention is based on the discovery of and isolation from Petunia (Mitchell) of highly efficient SSU promoter DNA, in particular the promoter DNA from the SSU gene denominated SSU301. The invention embraces the promoter DNA, DNA substantially homologous to the promoter DNA, and DNA at least in part substantially homologous to the promoter DNA. The invention further embraces the promoter in several forms: the promoter as an isolated 5' fragment of the SSU gene; the promoter as an isolated 5' fragment with the 3' end of the 5' fragment modified to create a restriction site which permits ready fusions with foreign structural genes; and the promoter in the form of an expression cassette comprising a 5' fragment of the SSU gene, a 3' fragment (preferably from the SSU gene), and a linker region connecting the two fragments. In particular, the invention is such an expression cassette where the fusion points between the 5' fragment and the linker region and between the 3, fragment and the linker region have been modified to create restriction sites which permit a foreign gene to be substituted for the linker so as to yield chimaeric genes containing the complete proximal 5' and 3' regions of the SSU gene but containing none of the DNA normally found between the translation start and stop sites of the SSU structural gene. The expression cassette of the invention preferably comprises at least 300 bp (base pairs) of both SSU 5' region and SSU 3' region. In a preferred embodiment the expression cassette of the invention contains a linker region bounded by 5' DNA and 3' DNA from SSU301, with an NcoI restriction site immediately upstream of the linker region and a BglII restriction site immediately downstream of the linker region (ATCC #67125). The invention also embraces chimaeric genes, or fused genes, resulting from the substitution via restriction enzymes of a foreign gene for the linker region of the expression cassettes of the invention. The invention further comprises expression vectors containing the expression cassettes of the invention or containing the expression cassettes of the invention with a foreign structural gene substituted in place of the linker region. In addition, the invention embraces the methods of preparing and using the promoters and expression cassettes of the invention.
BRIEF DESCRIPTION OF THE DRAWINGS
FIGS. 1A and 1B are a depiction of DNA sequence information for the 5' region of a gene for the small subunit of Petunia ribulose1,5-bisphosphate carboyxlase.
FIG. 2 is a depiction of DNA sequence information for the 3' region of a gene for the small subunit of Petunia ribulose-1,5-bisphosphate carboxylase.
FIG. 3 is a schematic showing the construction of an expression cassette of the invention.
FIG. 4 is a schematic showing restriction information for DNA constructs SSU3013 and SSU3014.
FIG. 5 is a schematic showing restriction information for recombinant plasmid pAGS007 containing an expression cassette of the invention (ATCC deposit #67125).
DETAILED DESCRIPTION
As used herein, the term "gene" means coding region together with associated 5, and 3, sequences. The term "structural gene" means coding region. The term "SSU gene" means the SSU structural gene plus an upstream DNA sequence (5' untranslated region) and a downstream DNA sequence (3' untranslated region). The upstream DNA sequence may also be referred to herein as the SSU promoter sequence, SSU promoter DNA, SSU promoter, SSU 5' sequences, SSU 5' region, SSU 5' fragment or SSU 5' flanking region. The upstream DNA sequence has one terminus corresponding to the nucleotide adjacent (on the 5' side) to the translation start site (ATG), and runs upstream from there. The downstream DNA sequence may also be referred to herein as the SSU 3' region, SSU 3' sequence, SSU 3' flanking region, SSU 3' fragment or SSU 3, tail. The downstream DNA sequence has one terminus corresponding to the nucleotide adjacent (on the 3' side) to the translation stop site (TAA) and runs downstream from there. The term "SSU structural gene" means a DNA sequence encoding the SSU precursor polypeptide, i.e., the SSU mature peptide plus the associated transit peptide. The DNA coding sequence has the translation start site at one terminus (5' terminus) and the translation stop site at the other (3' terminus).
A genomic library was constructed from DNA found in leaf cells of Petunia (Mitchell). The SSU301 gene and the SSU611 gene, along with five others from the group of eight SSU genes, were isolated from the genomic library using probes made from petunia SSU cDNA clones. The individual genes were identified after hybridization and high stringency washing to the different cDNA clones. The 5' and 3' ends of the isolated genes were sequenced using the dideoxy sequencing method. See Example II.
For purposes of evaluating promoter sequences of the invention, DNA probes were constructed specific to SSU genes found in the nuclear genome of Petunia (Mitchell). Probes made of 3' flanking regions discriminated among genes which were in what shall be referred to as three different gene families, namely, families corresponding to cDNA clones pSSU51, pSSU71 or pSSU117 (these gene families shall be referred to herein as, respectively, the 51 gene family, the 71 gene family, and the 117 gene family). As explained further below, the 51 gene family contains six of a total of eight SSU genes in petunia, the 71 gene family contains one SSU gene (SSU301), and the 117 gene family contains one SSU gene (SSU611). These probes were used to determine relative expression of the different gene families, based upon hybridization with mRNA. The highest level of steady state mRNA was found for mRNA corresponding to the gene for SSU301 (the sole gene in the 71 family). The second highest level corresponded to the gene for SSU611 (the sole gene in the 117 family). See Example III.
The sequence of the 5' untranslated region of the SSU301 an SSU611 genes, together with the corresponding regions of five others from the group of eight SSU genes, is shown in FIG. 1 (SSU491, SSU112, and SSU911 correspond to genes from the 51 family). The final three bases shown for the 5' region of each gene (lower right of FIG. 1) correspond to the translation start signal (ATG). The sequences for the different genes are organized so that the regions of homology are aligned. All of the sequences show an A or G positioned 3 bases upstream from the ATG start signal; this is believed related to efficient translation of a message. Regions which are conserved or semiconserved among the different 5' sequences are shown by underlining and numbering of block areas (numbers 1-17 on top of rows of sequences). Block 1 shows a putative TATA box homology. Since the TATA homology is normally positioned approximately 30 bp upstream from the transcription start, the 5' leaders (the segments between the transcription start and the translation start) appear to be fairly short (between 10 and 60 bp). The transcription start for the SSU301 gene is 54 bp 5' to the ATG translation codon. Block 7 shows a possible CCAAT box homology. There are also sequences containing homology to the `core` nucleotides of viral enhancer elements, e.g., block 8.
The sequence of the 3' untranslated region of the SSU301 and SSU611 genes, together with the corresponding regions of others from the group of eight SSU genes, is shown in FIG. 2 (SSU231, SSU491, SSUI112, SSU911 and SSU211 correspond to genes from the 51 family). The initial three bases shown for the 3' region of each gene (upper left of FIG. 2) correspond to the translation stop signal (TAA or TAG). Regions which are conserved or semiconserved among the different 3' sequences are shown by underlining and numbering of block areas (numbers 1-10 on top of rows of sequences). Block area 7 is likely a signal for polyadenylation. Differences in the 3' regions of the genes may lead to mRNA stability and thus affect the steady-state levels of mRNA.
It was initially demonstrated that the SSU promoter DNA of the invention functions upon reinsertion into plants in association with the wild type SSU structural gene. See Example IV.
It was subsequently demonstrated that the SSU promoter DNA of the invention can be used to control expression of foreign structural genes by introducing the promoter DNA and structural gene into the plant as a unit. This may be accomplished by fusing the promoter DNA directly to the structural gene prior to introduction into the plant. This is preferably done with the SSU promoter (in particular, the SSU301 promoter), not including the translation start codon at the promoter's 3' end, fused directly to the translation start codon of the structural gene. For this purpose the SSU promoter is preferably modified in advance to create a restriction site at the 3' end such that the applicable restriction enzyme will cleave at a point at or immediately upstream of the translation start codon in the wild type SSU gene (as explained further below in the discussion of expression cassettes). The fusion of the promoter DNA can either be to the structural gene containing its wild type 3' tail (if the structural gene is eukaryotic) or to a structural gene with a substituted 3' tail, preferably SSU 3' region and in particular SSU301 3' region. The SSU promoter DNA for use in fusion to a structural gene should be a segment at least 300 bp in length, and preferably at least 1000 bp in length. Longer lengths can effectively be used up to approximately 5000 bp. Even longer lengths can be used but may detract from experimental workability. If a substituted 3' SSU region is used in preparing the fused gene, this region should be at least 300 bp in length and preferably 1000-5000 bp in length.
In accordance with the invention, a preferred way to accomplish introduction of SSU promoter DNA and a foreign structural gene into a plant is to initially combine the foreign gene with an expression cassette comprising SSU promoter DNA (in particular SSU301 promoter DNA), a linker region fused downstream of the SSU promoter DNA, and SSU 3' region DNA (in particular SSU301 3' DNA) fused downstream of the linker region. In a preferred expression cassette, the 3' end of the promoter DNA and the 5' end of the 3' fragment are modified to create restriction sites such that the applicable restriction enzymes can cleave the cassette, respectively, at a point immediately upstream of the position of the translation start codon in the wild type SSU gene and at a point immediately downstream of the position of the translation stop codon in the wild type SSU gene. Hence the linker region may be removed by restriction enzyme cleavage and replaced by a fragment containing the gene to be introduced.
In the case of an expression cassette derived from SSU301, which is particularly preferred, the 3' end of the promoter can be modified in various ways to create a restriction site at the desired position. A preferred modification is to change the T nucleotide immediately upstream from the translation start codon of the wild type SSU301 gene to a C nucleotide, thereby yielding a six-base sequence CCATGG surrounding the translation start codon of the wild type SSU301 gene; this sequence corresponds to the restriction site for the restriction enzyme NcoI (see FIG. 3). Application of NcoI to a sequence so modified will cleave immediately upstream of the start codon (ATG) of the SSU gene. Other restriction sites could be created at the position just upstream of the translation start codon, with preferred modifications involving the fewest number of base changes. For instance, as will be understood by one skilled in the art, restriction sites specific to restriction enzymes NdeI or SphI could be created by appropriate DNA modifications (these enzymes also cleave around the sequence ATG which is the first codon of the coding region). Similarly, modifications can be made to the 5' end of the 3' fragment in an expression cassette derived from SSU301. A preferred modification is to change the T nucleotide two positions downstream from the translation stop codon of the SSU gene to an A nucleotide and to change the A nucleotide 4 positions downstream from the translation stop codon to a C nucleotide, thereby yielding a 6-base sequence AGATCT on the downstream side of the stop codon; this sequence corresponds to the restriction site for the restriction enzyme BglII (see FIG. 3). Application of BglII to a sequence so modified will cleave immediately downstream of the stop codon. Other restriction sites could be created at the position just downstream of the translation stop codon, with preferred modifications involving the fewest number of base changes. For instance, as will be understood by one skilled in the art, restriction sites specific to restriction enzymes EcoRV, HincII or HpaI could be created by appropriate DNA modifications. See Example V herein with respect to preparation of the particular preferred expression cassette referred to above.
Nucleotide modifications to the promoter and 3, sequences as described above are carried out using known techniques. Mutations are generated by known methods of site-directed mutagenesis using oligonucleotides (the sequences of which contain the desired mutation) and single stranded template DNA of the promoter and 3' sequences. See, e.g., M. J. Zoller et al., Nucleic Acids Res., 10, 6487-6500 (1982).
The linker sequence of the expression cassette of the invention is a noncoding segment of DNA inserted between the promoter region and the 3' region of the expression cassette. The sequence preferably has terminal restriction sites corresponding to those at the sites to which the linker is to be joined. Thus, for an expression cassette derived from SSU301 modified to have an NcoI restriction site at the end 3' to the promoter sequence and a BglII restriction site at the end 5' end to the 3' sequence, the linker would have a corresponding NcoI restriction site at one end and a corresponding BglII restriction site at the other. Ligation of the linker sequence to the end segments is by standard techniques. The length of the linker sequences is not critical; the length is preferably between 200 and 1000 bp.
The expression cassette contains at least 300 bp of promoter sequence upstream from the translation start site and at least 300 bp of 3' sequence downstream from the translation stop site, with at least 1000 to 1500 bp preferred in each case. Longer lengths can effectively be used in each case, up to approximately 5000 bp. Even longer lengths can be used in each case but may detract from experimental workability. The expression cassette preferably has a restriction site at each terminus (i.e., at the 5' end of the promoter sequence and at the 3' end of the 3' sequence) to allow the cassette to be separated from a vector as a linear DNA sequence.
A foreign gene may be introduced into the expression cassette of the invention in place of the linker sequence by cleavage of the expression cassette at the restriction sites on either side of the linker sequence and ligation of the foreign gene to the ends of the expression cassette so that the translation start codon of the foreign gene is proximal to, and preferably immediately adjacent to, the 3' end of the promoter sequence of the expression cassette and so that the translation stop codon of the foreign gene is proximal to, and preferably immediately adjacent to, the 5' end of the 3' sequence of the expression cassette.
Once the foreign gene is inserted in the expression cassette, the expression cassette can be introduced into an appropriate plant transformation vector, and plant transformation carried out using known techniques, e.g., with Agrobacterium. A plant so transformed will contain the foreign gene under transcriptional control of the SSU promoter. See Example VI.
The SSU promoters of the invention, in particular in the form of the expression cassettes of the invention, can be used to introduce foreign structural genes, regardless of type or source, into plants which are transformable.
A preferred expression cassette of the invention contains SSU301 promoter DNA (5000 bp approximately) with an NcoI restriction site at its 3' terminus, SSU301 3' region DNA (1500 bp approximately) with a BglII restriction site at the 5' terminus, and an intervening linker region (600 bp approximately). The expression cassette is bordered by BamHI restriction sites. Such a cassette is on deposit at the American Type Tissue Culture (deposit number 67125). The deposited microorganism is E. coli JM83-AMB007, a gram-negative, rod-type strain. This strain contains recombinant plasmid AGS007, which is a pUC plasmid (specifically, pUC12; J. Veira et al., Gene, 19, 259-268, 1982), carrying the expression cassette. See FIG. 5 for a schematic of plasmid AGS007 carrying the expression cassette. The expression cassette may be obtained from this deposited sample, as will be understood by those skilled in the art in view of the disclosure herein, by separating recombinant plasmid pUC12 from E. coli and isolating the expression cassette from the plasmid by using the restriction enzyme BamHI. If desired, the promoter sequence can be obtained from the expression cassette using the restriction enzyme NcoI and BamHI. This will yield restriction fragments of approximately 5, 2.7 and 2.1 kb. The 5 kb fragment will carry the promoter region. The linker region in the deposit is the 600 bp NcoI-BglII fragment from the NPTII gene carried on Tn5.
EXAMPLES
In general, preparation of plasmid DNA, restriction enzyme digestion, agarose gel electrophoresis of DNA, Southern blots, Northern blots after separation of the RNA on a formaldehydeagarose gel, DNA ligation and bacterial transformation were carried out using standard methods. Maniatis et al. (ed.), Molecular Cloning, a Laboratory Manual, Cold Spring Harbor Laboratory (1982).
EXAMPLE I
Isolation of SSU301 Gene
A. Plant material
The Petunia (Mitchell) strain is a doubled haploid produced by another culture from a hybrid between Petunia hybrida var Rose of Heaven and Petunia axillaris (A. Z. Mitchell, Dissertation, Harvard Univ., 1979). The plants were grown under greenhouse conditions.
B. Isolation of DNA
Petunia DNA was isolated as described in P. Dunsmuir et al., J Mol. Appl. Genet., 2, 285-300 (1983).
C. Preparation of Genomic Library
Petunia DNA was partially digested with Sau3A to give a mean fragment size of 15-20 kilobases (kb). The DNA was then fractionated on a 10-40% sucrose gradient with 1 M NaCl/20 mM Tris-HCl, pH 8/1 mM EDTA. The gradient fractions containing DNA fragments between 15 and 20 kb were concentrated with butanol and then by ethanol precipitation. Lambda phage EMBL3 DNA was completely digested with BamHI and then digested with a 10-fold excess of EcoRI. This step allows a biochemical selection against the reinsertion of the phage stuffer fragment during the ligation reaction. The small linker fragment was removed by isopropanol precipitation. A. M. Frischauf et al., J. Mol. Biol., 170, 827-842 (1983). The double-cut EMBL3 DNA was ligated to the fractionated petunia DNA in a 2:1 molar excess of EMBL3. Ligated DNA was packaged into lambda phage heads in 0.75 ug (EMBL3) aliquots using the Hohn and Murray procedure B. Hohn et al., Proc. Natl. Acad. Sci. USA, 74, 3259-3264 (1977). Two phage banks (200,000 recombinant phage) were screened by hybridization W. D. Benton et al., Science, 196, 180-182 (1977).
D. Preparation of Probes
Probes were prepared for use in isolating the SSU301 gene from the genomic library. The probes were of two types. The first type was the complete cDNA clone SSU71, the preparation and characterization of which is described in P. Dunsmuir et al., Nucleic Acids Res., 11, 4177-4183 (1983). The second type was the 3' untranslated region of the pSSU71 clone. The 3' region was obtained from the pSSU71 clone by restriction enzyme cleavage.
E. Isolation of Gene
The petunia SSU genes were isolated from a lambda phage genomic library using a petunia cDNA clone as a probe. See P. Dunsmuir et al., Nucleic Acids Res., 11, 4177-4183 (1983) regarding cDNA clone construction. The SSU301 gene was identified from the other genes by hybridization after high stringency washing to the SSU cDNA clone pSSU71. This was confirmed by using a probe which only contained the 3' untranslated region of the cDNA clone pSSU71.
EXAMPLE II
Sequencing of SSU301, 5' and 3' Regions
A. Method
The SSU genes, carried in the lambda phage clones described in C. Dean et al., Proc. Natl. Acad. Sci. USA, 81 4964-4968 (1985), Were subcloned into pUC plasmids (J. Vieira et al., Gene, 19, 259-268, 1982). These plasmids were linearized at unique restriction sites at one end of the rbcS genes. Progressive deletions into the genes were generated using Bal31 nuclease (N. E. Biolabs). Conditions were standardized so that approximately 200 bp/min were deleted. After phenol extraction the samples were then digested with a second restriction endonuclease which cut the insert out of the plasmid. The insert fragments were subcloned into M13 phage (J. Messing et al., Nucleic Acids Res., 9, 309-321, 1981) and the inserts were screened for their size. A range of inserts differing in approximately 100 bp were sequenced using the dideoxy sequencing method of F. Sanger et al., Proc. Natl. Acad. Sci. U.S.A., 74, 5463-5467 (1977). The procedure was repeated for the other DNA strand by linearizing the plasmid at a restriction site at the opposite end of the gene and then creating progressive deletions into the gene in the other direction.
B. Results
Sequence information is shown for the 5' untranslated region (FIG. 1 and the 3' untranslated region (FIG. 2) for SSU301, SSU611 and several of the SSU genes from the 51 gene family.
EXAMPLE III
Activity of Promoters
Relative activity of SSU promoters was determined by isolating and quantitating SSU mRNA.
A. Plant Material
The plant material was the same as in Example I. Leaf material used in RNA extractions was harvested from plants about 10 weeks old: only the top young leaves were used. The other organs of the plant used in RNA extractions were harvested from plants 18 weeks old.
B. RNA Isolation
Two g aliquots of the plant material from which the RNA was to be isolated were frozen in liquid nitrogen in a mortar and pestle and ground to a fine powder. 4.5 ml of NTES buffer (0.1 M NaCl, 0.01 M Tris-HCl pH 7.5, 1 mM EDTA, 1% SDS) and 3 ml of a phenol/chloroform solution [a 1:1 mixture of Tris-buffered (pH 8) phenol with chloroform/isoamyl alcohol (24:1)] were added and the grinding continued until the mixture thawed. The mortar was washed with 4.5 ml of NTES buffer and 3 ml of the phenol/chloroform solution. After vortexing for 5 minutes, the solution was centrifuged at 20,000 g for 10 minutes. The aqueous phase was removed and the phenol/chloroform layer was washed with 2 ml of NTES buffer. The combined aqueous layers were phenol extracted twice more. The nucleic acid was then precipitated by the addition of 0.1 vol. of 2 M NaAc and 2 vol. of ethanol. The precipitate was washed with 70% ethanol and then resuspended in 2.5 ml of sterile water. To remove DNA and low molecular weight RNA, an equal volume of 4 M LiAc was added and the solution allowed to sit for 3 hours on ice. The precipitate was pelleted at 10,000 g for 10 minutes. The pellet was resuspended in 0.9 ml of sterile water and the RNA was precipitated by the addition of 0.1 ml 2 M NaAc and 2 ml of ethanol. The pellet was washed with 70% ethanol and then resuspended in 0.1×SSC. The yield of RNA from 2 g of leaf tissue was approximately 4 mg.
C. RNA Quantitation
2.5 ug aliquots of each RNA sample or a dilution series of RNA from leaf tissue were denatured in 40 mM phosphate buffer pH 6.8, 6% formaldehyde for 30 minutes at 65° C. The samples were then adjusted to 1 m NH 4 Ac before loading onto a slot apparatus (8 ×1 mm slots). A sheet of Genescreen Plus (N.E.N.) rinsed in 1 M NH 4 Ac was placed immediately beneath the slots. Whatman 3MM paper and paper towels were used beneath the Genescreen Plus filter to draw the liquid placed into the slots through the Genescreen Plus filter. After addition of the RNA samples the slots were rinsed with 200 μl 1 M NH 4 Ac. The filters were dried and baked in a vacuum oven at 80° C. for 2 hours.
The 3' probes and the cDNA clone pSSU51 are inserts in the vector pUC9(J. Vieira et al., Gene, 19, 259-268, 1982) and can be cut out with a double enzyme restriction digest using EcoRl and HindIII. These were labelled with [alpha -32 ]daTP (400 Ci/mmol) using the T 4 polymerase procedure of P. O'Farrell, BRL Focus, 3, 1-3 (1981) after digestion of the clones with EcoRl. Following labelling, the clones were digested with HindIII to cut out the 3' tail sequences. The labelled inserts were purified on a 5% polyacrylamide gel. Using this method only the DNA strand complementary to the mRNA was labelled. The resection and filling in of the DNA was optimized to ensure labelling of the entire insert. This yielded probes of the same specific activity.
Prehybridization, hybridization and washing conditions were as described in C. Dean et al., Proc. Natl. Acad. Sci. U.S.A., 82 4964-4968 (1985). After exposure of the filters to Kodak X-ray film, the films were scanned densitometrically using a LKB Laser densitometer.
D. Results
The relative expression of SSU genes in Petunia leaf tissue is shown in Table I below.
TABLE I______________________________________ A B Hybridization Number of C To RNA cDNA Relative Expression (1) (2) clones of Each Gene (%)______________________________________SSU301 1 1 46.3SSU611 0.5 0.48 73 22.7SSU491 0.145 0.18 23 7.4 SSU112 17 6.9 0.15 0.16SSU911 0 N.D.SSU231 6 1.9SSU211 6 1.9SSU511 42 13______________________________________
Column A above shows the relative hybridization of the four rbcS 3' tail probes to petunia leaf RNA. Columns (1) and (2) summarize the results from two different RNA preparations. The gene showing the strongest hybridization signal is given the value of 1. The expression of the other genes is presented as fractions of this. The expression of the two rbcS genes SSU112 and SSU911 are given collectively, as the 3' tail probe 91A would hybridize to transcripts from both genes. Column B shows the number of cDNA clones isolated corresponding to each rbcS gene. These data were necessary to calculate the relative expression levels of the different rbcS genes because gene-specific probes could not be made for each individual gene due to the high degree of sequence homology. Column C shows the relative contribution of each rbcS gene to the total rbcS expression in leaf tissue (calculated from the data in columns A+B). N.D.=not detected. The genes SSU511 and SSU231 are indistinguishable over the sequence compared in the cDNA clone, hence individual expression levels could not be calculated for these genes.
Tests of relative expression of SSU genes in other Petunia organs (sepal, stigma/anther, petal, stem) gave results as shown in Table II below.
TABLE II______________________________________ Stig- ma/Gene Leaf Sepal Anther Petal Stem______________________________________SSU301 1 (1) 1 1 1 (1) 1 (1)SSU611 0.5 (0.44) 0.63 0.15 0.27 (0.56) 0.22 (0.17)SSU491 0.14 (0.18) 0.08 0.15 0.02 (0.06) 0.03 (0.04)SSU112 0.15 (0.15) 0.08 0.15 0.01 (0.02) 0.03 (0.02)SSU911______________________________________
The relative hybridization of the four rbcS 3' tail probes to RNA isolated from different organs of petunia is summarized above. The gene showing the strongest hybridization signal has been allotted the value of 1. The expression of the other rbcS genes is then presented as fractions of this. The numbers in the brackets show results from a second experiment. In each experiment alkali-hydrolyzed RNA was used as a control to ensure that only RNA was contributing to the hybridization signal. The expression of the two rbcS genes SSU112 and SSU911 are given collectively as the 3' tail probe 91A would hybridize to transcripts from both genes.
EXAMPLE IV
Reintroduction of SSU301 Promoter Associated with the Wild Type SSU Gene
The genomic clone SSU301 was introduced into binary vector pAGS135 by linearizing both plasmids at BamHI sites. The vector pAGS135 is the same as vector pAGS112 described in P. van den Elzen et al., Plant Molecular Biology, 5, 149-154 (1985) except that the unique XhoI site in pAGS112 has been removed by Klenow treatment of the linearized DNA and religation. Both orientations of the insert were conjugated into Agrobacterium tumefaciens LBA4404. The constructs pSSU3013 and pSSU3014 are illustrated in FIG. 4.
The constructs were introduced into tobacco cells by cocultivation and transformed calli were selected on kanamycin. Nine plants were regenerated for each construction and RNA was isolated from the young leaves after the plants had been in the greenhouse three weeks. The RNA was applied to slot blots and probed with the 3' specific probe 30A. Controls on the slot blot included non-transformed tobacco which showed that the 30A probe did not hybridize to tobacco RNA and untransformed petunia RNA which showed the endogenous level of SSU301 expression. Six of the 18 tobacco transformants showed levels of SSU301 RNA equivalent to that found in petunia. Seven of the 18 showed levels 50% or less than in petunia and 5 showed very low or undetectable levels.
EXAMPLE V
Construction of SSU Expression Cassette
With reference to FIG. 3, an SSU expression cassette (deposited as ATCC #67125) was prepared as follows. Restriction sites were created at the translation start point (NcoI at the ATG) and at the translation stop point (BglII just after the TAA) in the wild-type 302 gene. Two restriction fragments were subcloned from the wild type 301 gene into the bacteriophage M13mpll (J. Messing et al, Nucleic Acid Res., 9, 309-321, 1981). These restriction fragments were a 1.7 kb EcoRI fragment carrying the 5' end of the 301 gene and a 1.8 kb BglII - BamHI fragment carrying the 3' end of the 301 gene. Single-stranded DNA templates of both the 5' and 3' fragments were then isolated from the M13 phage particles and site-directed mutagenesis was carried out using oligonucleotides (the sequences of which contain the desired mutation); M. J. Zoller et al., Nucleic Acid Res., 10, 6487-6500 (1982). The mutations generated are illustrated below.
______________________________________5' 301 sequence TCTAACTATGGCTTC5' mutated sequence TCTAACCATGGCTTC3' 301 sequence GGCTTCTAAGTTATATTAGGA3' mutated sequence GGCTTCTAAGATCTATTAGGA______________________________________
Reconstruction of the 5kb 5' flanking DNA of the 301 DNA carrying the modification at the ATG was achieved by cloning the EcoRI fragment from the M13 phage into a plasmid (partially digested with EcoRI) carrying the upstream EcoRI fragment which had been modified in order to remove the NcoI site (NcoI digestion, Klenow treatment to fill in the overhanging sticky ends and religation). This cloning generated extra restriction sites at the 5' end of the 5' flanking DNA (from the pUC plasmid linker region) which included a BamHI site. The 5' flanking DNA can therefore be isolated from this plasmid on a BamHI-NcoI restriction fragment.
The 3' flanking DNA can be isolated from the M13 phage clone as a BglII-BamHI restriction fragment. These two fragments carrying the modified 5' and 3' flanking regions were cloned into the plasmid pUC12 using a 600 bp NcoI-BglII fragment of Tn5 as a linker. The Tn5 linker region does not contain any BamHI restriction sites.
To use the expression cassette, the plasmid is digested with the restriction enzymes NcoI and BglII and the desired coding region substituted for the linker fragment. The complete fragment carrying the 5' and 3' flanking regions and the coding region can then be cloned into Agrobacterium vectors on a BamHI, Sal-Xho or Sma-Xho fragment depending on the restriction sites in the coding region.
EXAMPLE VI
Introduction of Foreign Gene into Expression Cassette
In separate experiments, foreign structural genes were introduced into the expression cassette. The genes encoded octopine synthase, chloramphenicol acetyltransferase and chitinase.
A. Octopine synthesis
(1) Source and isolation of foreign qene
Octopine synthase (ocs) is an enzyme encoded on the Ti plasmid of octopine-type Agrobacterium strains. It is synthesized in tumors elicited by these strains on susceptible plants and the natural gene has an appropriate nucleotide sequence to constitute a weak, constitutive promoter in plant cells (H. DeGreve et al., J. Mol. Appl. Genet., 1, 499-511, 1983). The gene has been modified to remove all the promoter sequences and form an ocs "cassette" fragment which has been used to assay the strength of promoter sequences (L. Herrera-Estrella et al., Nature, 303, 209-213, 1983). If promoter strength is assayed by accumulation of chimaeric mRNA, fusions within the coding region give rise to more chimaeric RNA than the original ocs cassette. For this reason, in order to assay the strength of a chlorophyll a/b binding protein (cab) gene promoter, namely the cab 22L (P. Dunsmuir et al., Nucleic Acids Res., 13, 2503-2518, 1985) promoter, a construction was made in which the fusion point was within the ocs coding sequence. This construction served as the starting point for the ocs construction which was placed in the SSU expression cassette.
(2) Modification of foreign gene
An ocs cassette was cloned as a BamHI fragment into pUC8 so that the 5' end of the ocs gene was towards the Pstl site of the pUC linker. Ba131 deletions were generated from the Pstl site and BamHI linkers were ligated to the deletion endpoints. A deletion was identified by sequence analysis in which a BamHI linked had been placed near the beginning of the coding sequence. Sequence information is shown below.
______________________________________ocs wildtype ATG GCT AAA GTG GCA ATTocs deletion #133 CGGGATCCCGG GCA ATT______________________________________
The petunia cab 22L gene (P. Dunsmuir et al., Nucleic Acids Res., 13, 2503-2518, 1985) contains an NcoI site at the translational initiation codon and a PstI site 1 bp downstream (CTGCAG). Cab DNA was linearized at this PstI site, blunt-ended using T4 polymerase and then ligated to BglII linkers (CAGATCTG). The resulting construction was then ligated to ocs deletion #133 (a BglII site can be ligated to a BamHI site). The sequences of the initial cab 22L DNA and the two resulting constructions are shown below.
______________________________________cab 22L AAACC ATG GCT GCA GCTcab 22L- AAACC ATG GC CAGATCTGBglIIcab22L/ocs AAACC ATG GCC AGA TCC CGG GCA ATT______________________________________
The resulting chimaeric cab 22L/ocs construction thus introduces an NcoI site at the ATG of the ocs gene.
A BglII site was introduced immediately downstream of the ocs translation termination codon TGA by oligonucleotide site-directed mutagenesis (M. J. Zoller et al., Nucleic Acid Res., 10, 6487-6500, 1982). Sequence information is shown below.
______________________________________ocs 3' sequence TGGAGTTTGA ATCAAATCTTCocs 3' mutated sequence TGGAGTTTGAGATCTAATCTTC______________________________________
(3) Construction of the fusion
The ocs coding region was isolated by partial digestion with NcoI (to cleave the created NcoI site at the ATG but not the NcoI site within the coding region) and BglII digestion to cleave the introduced BglII site immediately downstream of the TGA. This was cloned into the SSU expression cassette which had previously been digested with NcoI and BglII. Both the 3' and 5' junctions of the SSU and ocs sequences were confirmed by sequence analysis.
B. Chloramphenicol acetyltransferase
(1) Source and isolation of foreign gene
Chloramphenicol acetyltransferase (CAT) is an enzyme that catalyzes the formation of acetylated derivatives of the antibiotic chloramphenicol. The gene encoding CAT was cloned from the bacterial transposable element Tn9 (C. M. Gorman et al., Mol. and Cell. Biol., 2, 1044-1045, 1982) and sequenced (N. K. Alton et al., Nature, 282, 864-869, 1979).
(2) Modification of foreign gene
Plasmid SV0CAT was used (C.M. Gorman et al., Mol. and Cell. Biol., 2, 1044-1045, 1982). This plasmid carries the CAT coding region on a HindIII - BamHI fragment. This fragment was cloned into the bacteriophage M13, and an NcoI site and a BglII site were introduced at the ATG and TAA respectively by oligonucleotide site directed mutagenesis. Sequence information is shown below.
______________________________________5' CAT sequence GGAAGCTAAAATGGAGAAAA5' mutated CAT GGAAGCTACCATGGAGAAAAsequence3' CAT sequence GGGCGTAA TTTTTTTAAGGC3' mutated CAT GGGCGTAAGATCTTTTTAAGGCsequence______________________________________
(3) Fusion construction
The CAT coding region (660 bp) was isolated by partial digestion with NcoI (to cleave the introduced site at the ATG but not the NcoI site within the coding region) and BglII digestion to cleave the introduced BglII site immediately downstream of the TAA. This was cloned into the SSU expression cassette which had previously been digested with NcoI and BglII. Both the 3' and 5' junctions of the SSU and CAT sequences were confirmed by sequence analysis.
C. Chitinase
(1) Source and isolation of foreign gene
The isolation of the chiA gene is described in J. Jones et al., EMBO J.,5, 467-473 (1985). The gene was isolated from a cosmid library of Serratia marcescens by virtue of the fact that the colonies caused clearing zones on chitin plates. A preliminary location of the coding region of the chiA gene on the cosmid was done by a deletion analysis of the cosmid clone and inspection of when the clearing zones on chitin plates disappeared. The accurate localization of the coding region was done by dideoxy sequence analysis.
(2) Modification of foreign gene and fusion construction
Modification of the 5' end of the chiA gene was done in several steps. An NdeI site was introduced at the ATG of the chiA gene by oligonucleotide site-directed mutagenesis (M. J. Zoller et al., Nucleic Acid Res., 10, 6487-6500, 1982). Sequence information is shown below. ##STR1##
The chiA gene was cut with NdeI and fused to a nopaline synthase promoter which also had an NdeI site at the ATG. Modifications of the resulting fusion were made using site-directed mutagenesis in order to improve the translation signals. Sequence information is shown below. ##STR2##
The modified nos-chiA fusion generated a BalI restriction site immediately downstream of the ATG. This was used to form a fusion with a chlorophyll a/b binding (Cab 22L) ocs fusion (see Section A of this Example) which had a BalI restriction site overlapping the ATG. Sequence information is shown below. ##STR3##
The resulting Cab-chiA fusion generated an NcoI site at the ATG. This was used to fuse the chiA coding region to the 5, end of the SSU expression cassette. Sequence information is shown below. ##STR4##
During the construction of the nos-chiA fusion, the chiA coding region fused to the nos 5' sequences was cloned as a BamHI (Klenow treated) EcoRV (partial digestion) fragment into the SmaI site of a pUC vector containing a TaqI fragment (in the AccI site) which carried the nos 3' region. The EcoRV site used was 25 bp downstream of the chiA translation termination codon. This fusion therefore added the nos 3' region onto the 3' end of the chiA coding region, completing the nos-chiA fusion. The resulting plasmid had a BamHI site (from the pUC linker) at the junction of the chiA and nos 3' sequences. This BamHI site was used to fuse the 3' flanking sequences of the SSU expression cassette to the chiA coding sequence (a BamHI site can fuse to a BglII site).
EXAMPLE VII
Plant Transformation with Expression Cassette Containing Foreign Genes
A. Cloning of modified expression cassette into vector
The CAT-SSU fusion was cloned into the binary vector pAGS135 (described in Example IV) on a BamHI fragment, and mobilized into the Agrobacterium strain LBA4404 (A. Hoekema et al., Nature, 303, 179-180, 1983). In a separate experiment the same procedure was followed for the chitinase - SSU fusion.
B. Plant transformation
The Agrobacterium strains were co-cultivated with protoplasts isolated from N.tabacum. (P. van den Elzen et al., Plant Molecular Biology, 5, 149-154, 1985). Transformed protoplasts were selected by their ability to grow on 50mg/1 kanamycin.
C. Expression of the SSU fusions in transformed plants
The transgenic tobacco plants were transferred to the greenhouse once they had established a good root system. They were assayed for expression three weeks after they had been in the greenhouse (previously established to be the time of maximal SSU RNA levels).
(1) CAT expression
The level of CAT RNA in individual transformed plants was assayed by primer extension. In this assay an oligonucleotide specific to the CAT RNA was annealed to total RNA and then extended in a reverse transcriptase reaction back to the 5' end of the message; the amount of extended fragment gave a measure of the levels of CAT RNA in the total RNA. Two of four tobacco transformants assayed, and one of three petunia transformants assayed, showed significant levels of CAT RNA.
(2) Chitinase expression
The level of chitinase RNA in individual transformed plants was assayed by primer extension (as described above). Ten plants were assayed. A range of RNA levels was observed. The relative RNA levels are summarized in the table below; the plant showing the highest levels of chitinase RNA was given the value 100.
TABLE III______________________________________Transformant No. Relative Chitinase RNA Level______________________________________1 102 1003 04 55 116 677 778 09 010 20______________________________________
A comparison of the chitinase RNA levels from plants transformed with nos-chi, Cab-chi and SSU-chi showed that on average the SSU-chi construct gave 200 times more RNA than the nos-chi constructs. The SSU-chi plant showing the highest chitinase RNA levels (No. 2) gave 15 times more RNA than the highest Cab-chi transformant.
The levels of chitinase protein as assayed by a Western blot (an antibody probe to a nitrocellulose filter carrying the size fractionated polypeptides) were high in six of the initial ten transformants assayed. They correlated with the levels of chitinase RNA observed in the individual transformants. The amount of chitinase protein was evaluated by including a standard dilution series of chitinase protein (isolated from a bacterial strain) on the Western blot. The SSU-chi plant (No. 2) which showed the highest RNA levels accumulated the chitinase protein to 0.1% of the total protein in the leaves. | Promoter sequences from the gene from the small subunit of ribulose-1,5-bisphosphate carboxylase are disclosed. Expression cassettes containing a promoter sequence, a linker region, and a 3' fragment are also disclosed. The promotor sequences and expression cassettes are useful for expressing foreign genes to high levels in transformed plants. | 2 |
BACKGROUND OF THE INVENTION
Present warhead concepts utilize single or multiple detonators which initiate the explosive at a point. Actually, the detonators initiate the explosive over a surface, but the surface area is so small in relation to the dimensions of the warhead that it is considered a point.
The warhead designer, working with point detonators, is limited in his choice of initiation schemes due to the physical size of the detonator. To initiate a warhead along any of several lines parallel to the axis and surface of the explosive charge requires relinquishing space that is normally used for fragments and using it for the detonators. Likewise, plane wave initiation cannot be incorporated in a device due to the large number of detonators needed. There do exist means for producing line or plane detonation waves which use only one detonator and a train of explosive, but these, however, are used for experimental studies and are too bulky for use in a warhead.
SUMMARY OF THE INVENTION
The warhead initiator system uses a helical fluxtrapper to explode a copper foil initiator which is embedded in a warhead. A helical fluxtrapper is a hollow metal rod filled with explosive and surrounded by a coil of wire. The coil of wire creates a magnetic field when current flows through it. Upon detonating the explosive the hollow rod expands and shorts out the coil, the energy stored in the magnetic field is converted to energy in the form of current.
The copper foil initiator is chemically etched to form many exploding bridgewire detonators. The foil is coated with a secondary explosive such as PETN and when current from the fluxtrapper is passed through the foil, the bridgewires explode and detonate the explosive simultaneously.
The entire system is small enough for inclusion in the ordnance section of a missile and allows for the warhead to be initiated by the foil at either a single point, several points, along a line or over a surface depending upon the foil geometry.
STATEMENT OF THE OBJECTS OF THE INVENTION
An object of the invention is to provide for simultaneous initiation at several points, along a line, or over a surface.
An object of the invention is that the initiator can be cast into the main explosive charge of a warhead.
Another object of the invention is that the initiator uses a negligible amount of volume so that neither fragments nor explosive need be sacrificed.
Other objects, advantages and novel features of the invention will become apparent from the following detailed description of the invention when considered in conjunction with the accompanying drawings.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic of the warhead initiation system.
FIG. 2A-C is a timing sequence of detonation and breakup of the warhead case in top and side views.
FIG. 3 is a sectional view of concentric initiator.
FIG. 4 is a sectional view of a line initiator.
FIG. 5 is a sectional view of a conical surface initiator.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The schematic of the warhead initiation system is shown in FIG. 1. A helical magnetic fluxtrapper power supply 10 is connected to an electrically exploded copper mesh initiator 20. The capacitor 11 is charged up by a small power supply 12. Switch 13 is closed allowing current from the capacitor 11 to flow through the helical coil 14 of the fluxtrapper, the copper mesh initiator 20 and the cylindrical armature 15. Switch 16 is then closed to take the capacitor 11 out of the circuit and simultaneously the detonator 17 is fired using power supply 18. The explosive 19 inside the armature detonates and causes the armature 15 to expand and short out the coils 14 of the helix from left to right. As the helical coils 14 are shorted out the inductance of the circuit is lowered and the current through the initiator 20 increases.
The copper mesh initiator 20 has a thin copper foil 21 which is chemically etched to form many small exploding bridgewires 22. The foil is coated with a secondary explosive 23. The initiator 20 is available, for example, from Sandia Corporation. When the current flowing from the fluxtrapper 10 through the initiator 20 reaches a critical value, the many bridgewires 22 explode simultaneously detonating the explosive 23. The bridgewires are separated from the return transmission line 24 by an insulating material 25.
The overall size of the copper mesh initiator can be varied to suit a particular application. Also the thickness of the foil 21 and the length, width and number of bridgewires 22 can be changed. Any of these changes must be accompanied by modification of the fluxtrapper 10 so that enough current will be delivered to the initiator 20.
FIG. 2 shows one use of the initiator system. In this configuration the initiator is used to control the fragment mass and shape of the warhead casing 30 upon detonation and subsequent breakup of the case. This is done by selecting the fragment mass and shape desired and designing the mesh pattern of the initiator so that upon detonation the detonation waves from each of the mesh points will collide along predetermined lines. This collision produces localized regions of high pressure and when the lines of collision reach the case wall they will cause the case to fracture along similar lines both in the longitudinal and transverse direction resulting in the fragment mass and shape desired.
FIG. 2A shows the warhead prior to detonation. The initiator 20 is embedded in explosive 31. The warhead is detonated at the initiation points 32. FIG. 2B shows the warhead during detonation. The detonation products 33 expand into the collision zone of detonation waves 34. FIG. 2C shows the case 30 fracture with the breakthrough of the collision zone 35.
The initiator 20 can be made thin enough so that it can be formed into a cylindrical or conical shape. It can also be placed in and surrounded by the main high explosive charge 31 of a warhead. In FIG. 3, any one of the several foil concentric cylinders 21 within a warhead can be initiated. The number and spacing of the bridgewires for each cylinder is chosen so that colliding detonation waves are formed upon detonation and fracture the warhead casing 30 into predetermined fragment sizes depending upon which cylinder is initiated. Utilizing this concept, one warhead can be used for different targets.
FIG. 4 illustrates initiation along any chosen line along the periphery of the warhead. This offers an aiming capability to the warhead. Any line or lines of initiation can be chosen to direct the fragments toward the target.
FIG. 5 illustrates the initiation of a conical surface within the warhead to give a "shape charge" effect.
Obviously many modifications and variations of the present invention are possible in the light of the above teachings. It is therefore to be understood that within the scope of the appended claims the invention may be practiced otherwise than as specifically described. | A warhead initiation system in which a helical magnetic fluxtrapper explo a copper mesh initiator at a single point, several points, along a line and/or over a surface. | 5 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention generally relates to data communications in a computer system and, more particularly, to memory control design to support synchronous Dynamic Random Access Memory (SyncDRAM) type memory.
2. Description of Related Art
In conventional central processing unit (CPU) designs, speed in which data is transferred within the CPU has been increasing rapidly with the advent Reduced Instruction Set Computers (RISC) architectures and even more so due to extensive use of pipelining. However, unlike the CPU development, development of different types of memory has concentrated on increasing media density in order to reduce the cost per bit of memory and not speed. This disparity has created an imbalance in memory bandwidth required for small low-cost systems. External interleaving to improve memory bandwidth has been employed to overcome this problem, but has failed. External interleaving has become a less favorable option due to use of asynchronous interfaces, high timing margins, high data rate, and a lack of registers for control signals, addresses and input/outputs. The cost of external interleaving is also high due to additional glue logic and total memory density required for a given bandwidth. This imbalance created the need for syncDRAM type memory units.
SyncDRAMs offer extensive memory density with low cost and high bandwidth memory architecture. Furthermore, syncDRAMs are able to support various applications like mainstore, peripherals, graphics and video. SyncDRAMs are designed for a wide range of applications with programmable features such as latency, burst length and burst-type. They can support single or dual bank high frequency and low power operations.
A key feature provided by syncDRAMs is immediate access to multiple blocks of data called "bursts." Burst length refers to the number of words that will be output or input in a read or write cycle respectively. After a read burst has completed, the output bus will become high impedance. The burst length is programmable as 1, 2, 4 or 8 words, or full page. The ability of the CPU to access these bursts of information gives the CPU access to wider bandwidth of memory.
The syncDRAM operates similar to its predecessor DRAM with further advanced features. Unlike conventional DRAMs, the syncDRAM is able to provide bursts of data in a series of 0 to 8 words in a single cycle or, when in page mode, can transfer a burst of an entire page to a destination unit. In a typical sequence, a microprocessor in the computer system will send a read or write request through the system bus to the memory control. The memory control will generate a signal which is sent through the DRAM bus to the syncDRAM for execution. Once the command is received by the syncDRAM, the syncDRAM proceeds with a preprogrammed sequence for transferring the data.
The syncDRAM must be initialized in the power-on sequence, much like conventional DRAMs, before data can be transferred. During initialization, the syncDRAM internal clock and data mask must be activated to avoid having data written into the syncDRAM during the sequence. There is typically a 100 ms delay that proceeds any commands being handled by the syncDRAM after the initiation sequence has begun. When asserting a command, a chip enable must be asserted so that commands are recognized by the syncDRAM for execution. Within the syncDRAM, commands executed correspond to the rising edge of the internal clock. When a command is sent to the syncDRAM, a clock enable signal (CE) allows the syncDRAM to receive the command and determine the validity of the next clock cycle. If the clock enable is high, the next clock rising edge is valid, otherwise it is invalid. If the clock rising edge is invalid, the internal clock is not asserted and operations in the syncDRAM are suspended. In conventional use, each time a command is asserted to the syncDRAM to transfer data, the chip must be initiated using the chip select and the clock enable in the same clock in order for the command to be recognized by the syncDRAM.
Once the chip is initialized with concurrent assertion of the chip enable and clock enable commands, data transfer can begin. When the address is valid, a page hit occurs and the syncDRAM is then ready to transfer data. The page is then indexed for specific data to be transferred. If an address request is invalid, however, a page miss occurs and a new page must then be opened to properly locate the requested data.
According to the preset burst rate, a series of words are then transferred to the syncDRAM unit in response to a write request or from the syncDRAM unit in response to a read request. In the case where data is not ready to be transferred, either in a read or write request, the syncDRAM continues to transfer the burst of data regardless of the data's readiness. In the case of a read request, data is continually read from an initial burst start address once initiated. Following the initial transfer of the word from the burst start address, an internal address incrementer in the syncDRAM increments the reading pointer to transfer consecutive words following the burst start address up to the end of the burst length preset by the DRAM whether the data path controller is ready to accept data or not.
Similarly, during a write sequence, after an initial word is transferred to the burst start address, the internal incrementer then increments the internal address to receive consecutive words following the burst start address in subsequent addresses regardless of whether or not data is ready at the sending device. The data path controller 18 determines whether data will be transferred.
In operation, the syncDRAM can be enabled by a command from a memory control unit responding to a data transfer request from the CPU. The syncDRAM responds with an initiation process that includes internally latching an address from which data will be read or written to. Each time a burst of data is requested, the syncDRAM must go through the initiation sequence in order to access the address from which data will be read or written. The time it takes to complete the initiation process will deficit the overall memory retrieval time needed to access the data.
Accordingly, it would be of great use to a computer industry to further speed up the already efficient syncDRAM memories by reducing the time it takes to access the syncDRAMs by reducing the time it takes to initiate the data retrieving cycle. In the event data is not ready to be transferred, conventional implementations require a second request to send data to or read data from the syncDRAM when the data is ready. This requires a subsequent read or write request which requires initializing the syncDRAM and opening a page again.
The operation of reading from the syncDRAM, in particular, requires not only initiating the syncDram, but also opening a particular page as well as the location on a page where specific data is located. To eliminate one or more of these steps in the reading operation would significantly speed up the reading operation, thus, making data available to the computer system much faster. As will be seen, the present invention in one embodiment, accomplishes this in a simple and elegant matter.
SUMMARY OF THE INVENTION
The present invention, in one embodiment, provides an interface and method for a synchronous DRAM (syncDRAM) memory that improve performance. In one embodiment, the read operation in a syncDRAM is significantly sped up by eliminating the step of opening a new page of data in a syncDRAM using a speculative read method. The embodiment provides the ability to open a page of information in the syncDRAM with a command generator in response to a data request. Speculative read logic is also included in the apparatus to continue reading from the page with an invalid address until a second read request occurs. Thus, in the event that a subsequent read request occurs that requests data located on the same page as the prior request, the data can be indexed and read from a location on that page without having to first assert the SCS# and SCAS#. This frequently removes the step of opening a page from the read process and, over time, can significantly speed up the overall syncDRAM reads in a computer system.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a general block diagram of a computer system employing a memory control of the prior art.
FIG. 2 is a general block diagram of a computer system in employing a memory control and a syncDRAM interface in accordance with one embodiment of the present invention.
FIG. 3 is a general block diagram of a main memory controller and a syncDRAM interface in accordance with one embodiment of the present invention.
FIG. 4 is a flow chart for describing functional aspects of one embodiment of the present invention.
FIG. 5 is a time diagram illustrating commands utilized in read requests in accordance with one embodiment of the present invention.
DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT
FIGS. 2-5 of the drawings disclose various embodiments of the present invention for purposes of illustration. One skilled in the art will recognize alternative embodiments that may be employed without departing from the principles of the invention that are illustrated by the structures and methods described and claimed herein.
The present invention provides a method and apparatus for controlling data transfer between a synchronous DRAM-type memory (syncDRAM) and a system bus. As can be seen in FIG. 1, a conventional computer system can have one or more nicroprocessors 10 communicating with the system bus 20. A conventional computer system further comprises various memory banks that can include syncDRAM memory. The microprocessors communicate with the syncDRAM memory 12 through memory control 14. Included in the memory control is a datapath 16 through which data is transferred from any one of the microprocessors to the syncDRAM 12 and a data path controller 18 that provides an interface among the datapath 16, the system bus 20 and a DRAM bus 22 that ultimately communicates with the syncDRAM memory 12.
In one embodiment of the present invention illustrated in FIG. 2, the advance memory control 24 operates similar to conventional memory controls with an included syncDRAM interface 26 for providing special controls during read cycles between the system bus 20 and the syncDRAM 12. The syncDRAM interface 26 is shown communicating with the data path controller 18 and the DRAM bus 22, with the DRAM bus 22 communicating with the syncDRAM 12.
Further details of the syncDRAM interface 26 are shown in FIG. 3. The interface 26 includes a command generator 28 communicating with the memory controller 18 and the DRAM bus 22, address incrementing logic 30 communicating with the memory controller 18, the command generator 28, the DRAM bus 22 and a mask generator 32 communicating with the data path controller 18, the address incrementing logic 30, the command generator 28 and the DRAM bus 22.
The command generator 28 is configured to produce commands to control the syncDRAM 12 of FIG. 2 including row address strobe (RAS#), column address strobe (CAS#) and write enable (WE#). A chip select (CS#) in the syncDRAM is controlled in conventional syncDRAM configurations internally and activated upon each data access to the syncDRAM. In one embodiment of the present invention however, CS# is held active low externally during read sequences. This allows for speculative reading of data as will be described in more detail below. These are standard commands that are recognized by syncDRAMs in their conventional implementation. These commands are similar to conventional DRAMs, but have additional functions. In a system where DRAMs and syncDRAMs are implemented among other types of memory in a single computer system, these commands may be distinguished by SRAS#, SCAS#, SWE# and SCS# respectively to associate the commands specifically with a syncDRAM in the system.
The syncDRAM interface 26 further includes address incrementing logic 30 that keeps account of the internal address incremented in the syncDRAM during a burst by holding the address received from the main memory control. This function will be described in further detail below.
Although the separate mechanisms of the SyncDRAM interface are illustrated in the abstract in FIG. 3 by block diagram, these separate mechanisms can be implemented using logic circuitry in the form of hardware as well as software used in conjunction with a microprocessor or controller. Many skilled in the art of computer design have available many methods to implement logic circuits to interface with a syncDRAM. The present invention, however, is not limited to any one particular configuration that falls within the scope of the claims below.
Details of the above described embodiment of the present invention is best described by its function as illustrated in the flow diagram of FIG. 4. This diagram will be discussed in conjunction with the two timing diagrams of FIG. 5 which show the sequence of commands executed in a syncDRAM with respect to time in the case of a read request.
Referring first to FIG. 4, in the first stage 35, the memory control determines whether the cycle is ready. The second stage 36 determines whether a syncDRAM burst is requested. In order for the interface to respond, a primary request must first be sent through the system to begin data transfer from the syncDRAM memory, a primary request being a read or write request originating from a microprocessor in the system and being sent through the system bus and the main memory controller to initiate the syncDRAM. It is important to note that a burst could be as few as one word of data. Once ready, the data retrieval process begins with a chip enable 37, then continues with an initial read data request 38 from the computer system into the syncDRAM interface. The next step 39 is to open a new page. In this step, the chip select (SCS#) and the row address strobe (SRAS#) are asserted and held low, and the column address strobe (SCAS#) is deasserted and held high. This step assumes that the page address is available and valid in the syncDRAM. The next step 46 is to index the open page where data is located. In this step, the bus SCS# and SCAS# are asserted and held low while the index address is available on address MA.
The next step 48 allows the system to sample the available data when available on the data bus MD. Once the data is sampled by the system, the next step 50 holds the page open while waiting for the next address by holding SCS# and SCAS# asserted low. This is distinguishable from conventional applications of syncDRAMs which typically pulse SCS# and SCAS# when opening a page. The conventional method requires that SCS# and SCAS# are asserted only when a new read is being initiated to the open page. The next data address is received in step 52.
Next is query 54 for determining whether the new address for the new data request is on the same page as the prior request. In accordance with the present invention, if the next address occurs on the same open page as the prior request, the syncDRAM interface simply indexes the same page by holding SCS# and SCAS# low when the next address is available on the address bus MA by returning to step 46. On the other hand, if the next address is not located on the same page as the prior request, the system returns to step 39 to open a new page by deasserting SCAS# and asserting SCS# and SRAS# low. The new page opens when the page address is available on the address bus MA. Once the cycle ends, the sequence returns to step 35 for a new cycle.
Now referring to FIG. 5, a contrast can be seen between the routing command sequence of the prior art with the new sequence according to one embodiment of the present invention. For purposes of clear illustration, it will be assumed for this discussion that the commands are asserted active low which is indicated on the timing diagram graphically where the active low step on a command line, is below the inactive step along the same time line. Also, the clocks indicate the rising edge of each signal that is synchronicity with a memory clock. Finally, the timing diagrams of FIG. 5 presume that the clock enable (CKE) signal is constantly asserted during the reading sequence.
Referring first to the prior art sequence 70, it can be seen that the initial step occurring on clock number 1 is a page open step where the SCS# signal 72 and the SRAS# signal 74 are asserted together active when an address is available on the address bus MA 76. Data is indexed on the open page of the syncDRAM by then asserting the SCS# signal 72 along with the SCAS# signal 78 in clock cycle 4. With the column address strobe now pointed to the data, data is then available on clock 6 for the system to sample and read the data D0'.
If a second request occurs and the data is located on the same page, the SCS# signal 72 and the SCAS# signal 78 are again pulsed active on clock number 8 giving the second block of data D1' on clock number 10. As with both data requests, the data is available for sampling by the system two clock cycles after the SCS# 72 and SCAS# signal 78 are asserted. Again, for the second request, the address for the data must be available on the address bus MA 76 in clock 8 in order for a page to be indexed on clock 8 and for data to be available on the data bus MD 80 two clocks later.
Referring now to the new sequence 90, it can be seen that the first page is open in the same matter as the prior art. As in the prior art, the new information, in accordance with the present invention, asserts the SCS# 92 along with the SRAS# 94 while the page address is available on address bus MA 96. The page is then indexed by asserting the SCS# signal 92 along with the SCAS# signal 96 when the index address A0 is available on the address bus MA 98 in clock cycle 4. The data D0 is then available two clocks later on the data bus 100 for the system to sample.
In this new sequence, in accordance with the present invention, the SCS# 92 and the SCAS# 96 are held active by asserting them low until a new address is available on the address bus MA 98. The next address A1 being available on the address bus MA 98 in clock 7 then gives data two clocks later on the data bus MD 100 on clock number 9. As can be seen in comparison with the prior art sequence, D1 is now available one clock earlier than D1' in the prior art sequence 70. This is where the savings is recognized in the event that the index address is on the same page as the prior indexed address. Statistically, this can occur in as much as 50% of the read sequences in a typical system, giving a great deal of savings in time for memory reads.
In the event that the speculative read is attempted and the next address request is for data located on a different page, a page miss must occur and a new page must be opened. In this event, the SCS# signal 92 is maintained active and the SRAS# signal 94 is pulsed active to access a new page. The next address can then be indexed on a subsequent clock giving data that occurs three clocks from the previous data read. This is exactly what would occur in the prior art sequence 70 in the event of a page miss.
Thus, in the event that a page hit occurs where two consecutive addresses occur on the same page, one clock is saved. Whereas, in the event that a page miss occurs where two consecutive address are located on different pages, no time loss occurs in retrieving data in comparison to the prior art sequence 70. In other words, if consecutive data requests occur for data located on a common page in the syncDRAM, one clock is saved. Conversely, if consecutive data requests occur for data located on different pages, only a single clock cycle is required to retrieve the data, giving accessibility to the data in the same amount of time as the prior art sequence 70.
From the above description, it will be apparent that the invention disclosed herein provides a novel and advantageous method and apparatus for controlling data transfer between a synchronous DRAM-type memory and a system bus. As will be understood by those familiar with the art, the invention may be embodied in other specific forms without departing from its spirit or essential characteristics, and thus, the described embodiment is not restrictive of the scope of the invention. The following claims are indicative of the scope of the invention, and all variations which come within the meaning and range of equivalency of the claims are to be embraced within their scope. | An interface and method for a synchronous DRAM (syncDRAM) memory are provided that improve performance. The read operation in a syncDRAM is significantly sped up by eliminating the step of opening a new page of data in a SyncDRAM using a speculative read method. This provides the ability to open a page of information in the SyncDRAM with a command generator in response to a data request. Speculative read logic is also included to continue reading from the page with an invalid address until a second read request occurs. Thus, in the event that a subsequent read request occurs that requests data located on the same page as the prior request, the data can be indexed and read from a location on that page without having to first assert the SCS# and SCAS#. This frequently removes the step of opening a page from the read process and, over time, can significantly speed up the overall SyncDRAM reads in a computer system. | 6 |
This invention relates to the gaseous reduction of particulate iron ore to sponge iron in a vertically arranged, moving bed reactor, and more particularly, to a novel way of operating such a reactor that is especially useful in those cases where the reducing gas for effecting the reduction of the ore is produced by gasifying a carbon-containing fuel, i. e. a carbonaceous solid or liquid.
BACKGROUND OF THE INVENTION
The direct reduction of iron ore in vertical shaft, moving bed iron ore reduction reactors has long been known. Representative processes for effecting such gaseous reduction are disclosed, for example, in U.S. Pat. Nos. 3,765,872; 3,779,741; 4,150,972; 4,216,011; and 4,338,123. In such systems reduction of the ore has commonly been effected by a reducing gas largely composed of carbon monoxide and hydrogen obtained by catalytic reformation of a mixture of natural gas and steam. In such systems the ore to be reduced is typically fed to the top of a vertical shaft reactor and flows downwardly through a reduction zone thereof in contact with an upwardly flowing hot reducing gas to convert the iron ore to sponge iron. Effluent gas from the reduction zone of the reactor is cooled to remove water therefrom, and in most cases a major part of the cooled effluent gas is reheated and recycled to the reducing zone. At its lower end the reactor is provided with some means for controlling the discharge of sponge iron from the reactor, e.g. a rotary discharge valve, a vibratory chute, conveyor belt or the like.
Catalytic reformers for producing the carbon monoxide/hydrogen reducing gas mixtures for use in such moving bed reactors are relatively expensive and natural gas used as a feed material for the reformer is not always readily available at an acceptable cost. Hence it has been proposed that the reducing gas be generated in a coal gasifier, for example, a melter-gasifier of the type in which powdered coal and an oxidant gas are fed to a molten metal bath. The coal is partially burned by the oxidant gas, advantageously oxygen, to generate heat that maintains the bath molten and to produce a reducing gas suitable for use in the ore reduction reactor. The ash from the combustion of the coal is removed from the gasifier periodically or continuously as a molten slag. Suitable melter-gasifiers of this type are known in the art.
While in general coal gasifiers provide a relatively inexpensive source of reducing gas, their use leads to certain other operating problems. Thus the gas generated in the gasifier is relatively dusty and the dust tends to clog the interstices between the ore particles in the reactor. If the gas is scrubbed with a scrubbing liquid to remove the dust, its sensible heat is lost and the gas must be reheated before being introduced into the reactor. Also, one of the problems encountered in the operation of a moving bed reduction reactor is the tendency of the ore particles to agglomerate and form large aggregates and such agglomeration impedes the flow of solids through the reactor
SUMMARY OF THE INVENTION
It is accordingly an object of the present invention to provide a method for the gaseous reduction of iron ore that is especially useful in cases where the reducing gas is derived from the gasification of coal or other carbon-containing fuel. It is another object of the invention to provide an ore reduction process of this type which permits the use of a dusty reducing gas while overcoming the clogging and agglomeration problems referred to above. It is still another object of the invention to provide in a moving bed gaseous reduction reactor a novel type of gas outlet structure having a renewable gas/solid interface that eliminates the accumulation of fine particles and consequent partial blockage of the gas outlet that sometimes occurs in prior art reactors. It is a further object of the invention to provide a method for reducing iron ore to sponge iron in a vertical moving bed reduction reactor, which method produces a smaller proportion of fines than prior methods. Other objects of the invention will be in part obvious and in part pointed out hereafter.
The objects and advantages of the invention are achieved in general by reversing the normal direction of flow of the ore particles through the reactor, i. e. by using an upwardly moving bed of ore particles and a downward flow of the reducing gas. The ore particles are forced upwardly through the reactor shaft counter-current to the descending reducing gas and the reduced ore, e. g. sponge iron pellets, pass over the upper periphery of the reactor and are removed therefrom by gravitational flow. The reactor wall diverges outwardly and upwardly to facilitate flow of solids therethrough.
With this mode of operation dust-laden gas can be used without causing blockage problems. To the extent that dust accumulates in the ore body it is carried continuously upward and discharged with the reduced ore at the top of the reactor. In like manner, fine material formed due to interparticle abrasion in the moving bed, as well as particle aggregates formed by the agglomeration of particles within the reactor, are carried upward for discharge at the top of the reactor and do not impede the flow of solids or gases as they sometimes do in a downwardly moving ore bed.
In recent years it has become increasingly common to pelletize the iron ore before feeding it to a moving bed reactor because the iron ore pellets are stronger than lump ore and have less tendency to disintegrate into undesired fine particles. The ore pellets are also stronger than the product sponge iron pellets formed by reduction of the ore pellets. In a conventional reactor with a downwardly moving bed the relatively weak sponge iron pellets are the bottom of the bed and subject to the pressure exerted by the total weight of the bed which tends to promote their disintegration. With the upflow bed of the present invention the relatively strong ore pellets are at the bottom of the bed and the relatively weak sponge iron pellets are near the top of the bed. Thus with an upflow bed there is less tendency to produce fines.
The upflow bed is also advantageous from the standpoint of minimizing agglomeration of the pellets. Increasing pressure tends to promote agglomeration of the hot pellets in the moving bed. With an upflow bed the hottest pellets are at the top of the bed where the pressure from overlying pellets is minimal.
The upward divergence of the reactor wall in combination with an upflow bed is advantageous in respect to both the pellet disintegration and the pellet agglomeration problems. In conventional downflow reactors there is usually at least one level at which the pellet flow path converges, thus increasing the inter-pellet pressure. With the reactor of the present invention such increases in the inter-pellet pressure are avoided.
BRIEF DESCRIPTION OF THE DRAWING
The objects and advantages of the invention can be more fully understood and appreciated by reference to the accompanying drawing which schematically illustrates a reduction system wherein iron ore to be reduced flows upwardly through a vertical shaft reactor countercurrently to a downwardly flowing stream of hot dusty reducing gas produced from coal in a melter-gasifier.
DETAILED DESCRIPTION OF EMBODIMENTS
Referring to the drawing, the numeral 10 generally designates a vertical shaft reduction reactor through which a bed of particulate iron ore 11 is forced upwardly. The reactor 10 comprises an upper section 12 and a lower section 13, both of which have an inverted conical configuration. The upper end of section 13 extends into the lower end of section 12 to define an annular discharge opening 14 through which spent reducing gas leaves the reactor, as more fully described below.
Iron ore to be reduced is stored in a bin 15 from which it flows by gravity through a conduit 16 to a feed chamber 18 and more particularly, to a feed mechanism located within the feed chamber and generally designated by the numeral 20. The mechanism 20, which may be of the general type described in U.S. Pat. No. 2,627,455, operates to transfer ore from the discharge end of conduit 16 to the bottom of bed 12 and force the ore particles upwardly through shaft reactor 10.
As shown in the drawing, the feed mechanism comprises a feed tube 22 pivotally mounted at its lower end by pivot 24 to the floor 26 of chamber 18 and having at its upper end a baffle 28 curved to conform with the curvature of the top 30 of chamber 18. Within the feed tube 22 there is a reciprocable piston 32 that can be moved axially of the feed tube by a first hydraulic cylinder 34. A second hydraulic cylinder 36 interconnects the feed tube 22 with the side wall of chamber 18 in such manner that operation of cylinder 36 causes the feed tube to be rocked around pivot 24.
When feed tube 22 is in its vertical position as shown in the drawing, it is in axial registry with the bottom end of shaft 13, and the right-hand portion of baffle 28 is positioned to block the discharge end of feed conduit 16. Hydraulic cylinder 36 is operable to cause the feed tube 22 to rock on pivot 24 until it is in axial registry with feed conduit 16 and the left-hand portion of baffle 28 is positioned to block the lower end of shaft 13. In operation the feed tube is positioned by the hydraulic cylinder 36 in registry with conduit 16, and hydraulic cylinder 34 is operated to withdraw piston 32 into feed tube 22 and permit a charge of ore particles to flow into the feed tube. Hydraulic cylinder 36 then rocks the feed tube back into its vertical position and cylinder 34 is operated to cause piston 32 to force the charge of the ore particles into the bottom of shaft 13. Repetitive charging and discharging of the feed tube in this manner causes the particulate bed 12 to move upwardly through shaft 13.
Reducing gas for reducing the ore to sponge iron is generated in a melter-gasifier 40 which may be of a suitable and well known type wherein a bath of molten iron 42 is used as a reaction medium and powdered coal and oxygen are fed to the bath in such proportions as to generate a reducing gas. More particularly, powdered coal is supplied to the melter-gasifier through supply pipe 44 and branch pipes 46 and 48, and oxygen is supplied through supply pipe 50 and branch pipes 52 and 54. Within the gasifier the coal is partially burned to maintain the reaction bath 42 molten and to generate a reducing gas largely composed of carbon monoxide and hydrogen. The ash content of the coal accumulates as a molten layer 56 on the top of the molten iron bath 42 and is removed intermittently or continuously through pipe 58.
At the top of the reactor 10 there is a gas inlet chamber or plenum 60 through which reducing gas flows to the top of the ore bed 12 and thence downwardly through the bed to reduce the ore to sponge iron. The gas feed to the inlet chamber comprises a mixture of recycled gas from pipe 62 and make-up gas supplied from the gasifier 40 through pipe 64. To promote mixing of the two gas streams a Venturi-type injector 68 is used comprising a nozzle 70 which receives recycle gas at an elevated pressure from pipe 62 and forms a jet that draws in hot gas from the gasifier discharge pipe 64. The injector 68, in addition to promoting mixing of the gas streams, also reduces the pressure at the discharge end of pipe 64 and thus permits the reactor to operate at a higher pressure than the gasifier.
The reducing gas mixture, preferably at an initial temperature of 700° to 900° C., flows downwardly through the ore bed 11, reducing the ore particles therein to sponge iron, and thence through annular discharge opening 14 into a gas outlet plenum 74. Most of the spent gas leaving the reactor is upgraded and recycled thereto. In particular, gas is withdrawn from plenum 74 through pipe 76 and flows successively through a cooler 78, wherein it is de-watered, pipe 80, pump 82, pipe 84 and carbon dioxide absorber 86. The resulting upgraded gas flows through pipe 88 to a heater 90 which re-heats the gas. The outlet of the heater is connected to pipe 62 referred to above. A portion of the recycled gas is withdrawn from pipe 80 through branch pipe 94 containing regulating valve 96 and used as a fuel gas in heater 90. To the extent that gas may accumulate in excess of that consumed in the system, it may be withdrawn from pipe 84 through a pipe 124 and branch pipe 92 and conducted to a suitable point of use or storage.
Reverting now to the configuration and function of the gas outlet plenum 74, there is a tendency for the discharge opening 14 to become partially clogged over a period of time and interfere with the free flow of gas therethrough. To deal with this problem the annular opening 14 and plenum 72 are constructed and arranged to provide for a continual renewal of the ore/gas interface in the plenum. In particular, the plenum 74 has a conical bottom 100 leading to a duct 102 terminating at the rotary discharge valve 104. Ore particles flowing through the opening 14 initially assume a normal angle of repose in plenum 74 and have a free upper surface 106 through which the exiting gas flows. Periodically, or continuously if desired, the rotary discharge valve is operated to cause particles to flow from plenum 74 downwardly through duct 102, whereupon a further quantity of ore particles flows through the discharge opening 14 to renew the surface 106. As indicated by the dotted line 107, particles discharged through valve 104 can be returned to the storage bin 15.
As generally described above, the ore bed 11 is forced upwardly through the reactor 10 and the particles thereof are reduced by the downwardly flowing hot reducing gas to sponge iron, which is then removed from the reactor. More particularly, the chamber 60 is provided with a conical bottom 110 and sponge iron particles reaching the top of reactor 10 overflow its upper perimeter 111 into this conical portion 110 of chamber 60 and thence through a duct 112 to the gasifier 40 wherein they are melted by the heat generated by the reaction of coal and oxygen in the gasifier. Molten metal can be removed from the gasifier, either continuously or intermittently, through pipe 113 and used, e. g., as a charging stock for a steel-making furnace.
In cases where it is desirable to store the sponge iron product or transport it to a remote location, the particulate product may be cooled and briquetted. Apparatus for performing such a briquetting operation is illustrated in dotted lines in the drawing. In accordance with this alternative, sponge iron pellets flow from the conical bottom 110 of chamber 60 throu9h a duct 114 to a briquetting chamber 116. Within chamber 116 there are a pair of pressure rolls 118 for converting the sponge iron into briquettes that are discharged from chamber 116 at 120. In cases where the reactor operates at an elevated pressure, a pressure lock or seal 117 is used at the discharge end of chamber 116. Also, when pressure operation is used, suitable locks or seals of known construction are required in conduit 16 and duct 102, and the feed chamber 18 is desirably pressurized with an inert gas through connection 122.
If it is desired to cool the sponge iron particles descending through duct 114 before they are discharged, such cooling can be accomplished by diverting a small amount of recycle gas flowing through pipe 84 to pipe 124 which contains regulating valve 126 and is connected to the bottom of duct 114 in such manner that the recycle gas flows upwardly through the duct and cools the descending sponge iron particles.
From the foregoing description it should be apparent that the present invention provides a process for the gaseous reduction of iron ore capable of achieving the several objectives recited above. By using an upwardly moving bed the problems of clogging due to fines and agglomeration of particles into large aggregates, both of which tend to impede solids and/or gas flow through the reactor, are largely overcome, since any aggregates formed are carried upwardly through a shaft of increasing cross-sectional area having an unobstructured upper perimeter over which the aggregated material can flow. Hot dust-laden gases can be used without difficulty since much of the dust is screened out in the upper portion of the bed and carried upwardly out of the reactor.
It is, of course, to be understood that the foregoing description is intended to be illustrative only and that numerous changes can be made in the system described within the scope of the invention as defined in the appended claims. | Particulate iron ore is reduced to sponge iron in a vertical shaft reduction reactor by forcing the ore upwardly in a moving bed counter-current to a descending stream of hot reducing gas produced by the gasification of coal in a gasifier, for example, a melter-gasifier, containing a molten iron bath and producing a hot dust-laden gas. The product sponge iron may be used as a feed material for the molten bath in the gasifier. The reactor is equipped with a gas outlet plenum containing a renewable body of ore to minimize clogging at the gas outlet. | 2 |
BACKGROUND OF THE INVENTION
1. Field of the Invention
The present invention relates particularly to a control system for controlling the ignition timing of a spark-ignition internal combustion engine, having a crankshaft, and more particularly to an improved electronic ignition control circuit for advancing or retarding the ignition timing in response to the rotational speed of the crankshaft.
2. Description of the Prior Art
The conventional ignition timing control systems of the kind comprise a centrifugal spark advance mechanism for adjusting the ignition timing of an engine according to the number of revolutions of the engine and a vacuum control mechanism adapted to advance or retard the ignition timing according to the engine intake manifold vacuum. This is based on the concept that primarily the ignition of an engine can be accurately timed to a satisfactory degree according to two factors: the engine revolutions and engine intake manifold vacuum.
With the conventional ignition timing control systems described above, a spark advance characteristic curve corresponding to the engine rpm is obtained by means of the centrifugal spark advance mechanism and then a parallel displacement of this spark advance characteristic curve is effected by the vacuum control mechanism according to the engine intake manifold vacuum so as to obtain a desired ignition timing.
Furthermore, when the conventional ignition timing control system is used in race boats, race cars and other applications of the internal combustion engine it utilizes a distributor, a magneto or a magnetic or optical device to monitor the position of the crankshaft directly. The system that uses the distributor for the timing function is capable of varying the amount of timing advance and does so by a mechanical device involving the use of a transducer, such as an electrical transducer, a mechanical transducer or a vacuum transducer. None of these transducers provides to a high degree accurate control of the advance function; and none of these transducers provide flexibility in the type of advance characteristics that may be obtained.
Presently, timing systems that employ computers to modify the advance characteristics of the ignition timing are made less accurate by the fact that they still use transducers to modify the spark timing function. A timing system utilizing a distributor to obtain its basic timing function also utilizes mechanical points, magnetic proximity detectors or optical pick-off devices. This timing system employs a mechanical device to vary the spark timing. There is a disadvantage in using the distributor to obtain the basic timing function in that there is a significant error between the position of the distributor shaft and the position of the crankshaft. The distributor's position error is caused by the slack between the crankshaft, camshaft and the distributor shaft. Since the position of the crankshaft is the important factor in timing the spark for optimum horsepower, optimum efficiency, minimum exhaust emissions or whatever engine characteristic is most desirable for the particular application for which it is being used it is desirable to eliminate or reduce the distributor's position error relative to the crankshaft.
A small number of timing systems presently in use actually "time" directly off the crankshaft, using it as a basic timing reference device by using a magnetic or an optical device. While this eliminates the error in the basic timing function, it renders the normal advance-modification techniques useless.
There are also mechanical timing systems that employ a centrifugal device and/or a vacuum control device, but these systems are cumbersome and exhibit poor accuracy, thereby defeating any advantage that may be gained by employing the crankshaft itself as the basic timing reference. Furthermore, these timing systems offer very little flexibility in the spark advance characteristics that may be obtained.
There are some devices in the prior art that obtain a spark timing which is accurate to a high degree and that provide flexibility in the spark advance characteristics that may be obtained. For example, U.S. Pat. No. 3,871,342 entitled Electronic Ignition Timing Control Circuit For Internal Combustion Engine, issued to Hiroshi Fujinami and Katuyuki Takagi on Mar. 18, 1975 teaches an electronic timing control circuit that uses a digital device primarily in its computing circuits to provide stability against variations in both voltages of the power supply of the control circuit and the ambient temperature. This control circuit is too cumbersome to provide the most effective and reliable device to achieve an optimum timing function. Furthermore, this control circuit requires, in addition to reference angular detecting device, a separate revolution detecting device.
U.S. Pat. No. 3,768,451, entitled Ignition Timing Control System, issued to Hisaji Okamoto on Oct. 30, 1973, teaches an ignition timing control system having a set of ignition times present to meet the ignition timing requirement of an engine operating under various satisfactory operating conditions, whereby an ignition time which meets the ignition timing requirement of the engine at each time is selected from the set of ignition times to be applied to the engine according to the engine revolutions, engine intake manifold vacuum, and temperature of the engine cooling water. This ignition control system is too cumbersome to be practical.
U.S. Pat. No. 3,853,103, entitled Ignition Timing Control System for Internal Combustion Engine Ignition Systems, issued to Joseph Wahl and Wolf Wessel on Dec. 10, 1974, teaches an ignition timing control system having a pulse generator which provides a pulse train representative of angular position of the engine crankshaft, and a marker pulse, at a predetermined angular crankshaft position. A counter is connected to the train of pulses to start counting upon occurrence of the marker pulses. A digital/analog converter converts the binary count numbers into an analog signal, which is compared with engine operation signals representative of spark advance or retardation, the comparator providing an output when the count derived from the counter and the operation parameter control signals match. The engine operation control signal may be a composite of signals commanding spark advance or spark retardation, such as speed signals, load signals or other operating parameter signals, applied to the comparator as varying voltages or currents. This design is too cumbersome to be practical.
SUMMARY OF THE INVENTION
In view of the factors and conditions characteristic of the prior art it is a primary object of the present invention to provide an improved ignition timing control system which can be incorporated on an engine without any material modification of the engine other than mounting a sensor to monitor the position of the crankshaft of the engine and a target mounted to the crankshaft of the engine.
It is another object of the present invention to provide an improved ignition control system which can provide a change of ignition timing by an operator performing a few simple adjustments to the control circuitry of the ignition control system, such as adjusting one of the potentiometers.
It is still another object of the present invention to provide an improved ignition control system which can provide ignition timing characteristics which are independent of environmental conditions and independent of such internal conditions as engine temperature, voltages of the power supply, and tolerances of resistors and other components used in the control circuit.
It is yet another object of the present invention to provide an improved ignition control system that is flexible in providing timing characteristics with few components and in still being maintained to a high degree of timing accuracy.
It is yet still another object of the present invention to provide an improved ignition control system that achieves the desired timing characteristics without using moving parts within the control system, yet with still using the distributor rotor as a spark sequencer.
In accordance with an embodiment of the present invention a spark timing computer, for use in a system for advancing or retarding the spark timing of an engine having a set of spark plugs, a spark generator for generating a pulse in response to a spark trigger, a coil for generating a spark in response to the pulse, a distributor for distributing the spark to each of the spark plugs, with the engine also having a crankshaft and a reference angle detecting device coupled to the crankshaft and having a square wave output, has been described. The spark timing computer includes a resetting device for forming a start pulse and a stop pulse which is electrically coupled to the reference angle detecting device, and integrator which is electrically coupled to a voltage reference and which is reset by either a stop pulse or a start pulse from the resetting device, a peak detecting device which is reset by the resetting device for detecting and holding the peak amplitude of the peak detecting device, a scaling device for scaling the peak amplitude of the peak detecting device which is electrically coupled to the peak detecting device, a comparing device for comparing the scaled peak amplitude of the peak detecting device with the output signal of the integrator and a triggering device for forming a spark trigger in response to a signal from the comparing device and for sending the spark trigger to the spark generator. The spark timing computer also includes devices for varying the stop pulse width and the start pulse width which are electrically coupled to the resetting device. The spark timing computer further includes a triggering device for providing a spark trigger in response to the start pulse of the resetting device and an inhibiting device for inhibiting the triggering device in response to a signal from the peak detecting device indicating a particular rotational speed of the engine. The spark timing computer has a set of devices for introducing steps in the advance and retard characteristics of the spark timing. In order to control the width of the spark trigger the spark timing computer uses a monostable multivibrator which is electrically coupled to the comparing device so as to provide a consistent spark trigger characteristic.
The features of the present invention which are believed to be novel are set forth with particularlity in the appended claims.
Other objects and many of the attendant advantages of this invention will be more readily appreciated as the same becomes better understood by reference to the following detailed description and considered in connection with the accompanying drawing in which like reference symbols designate like parts throughout the figures.
DESCRIPTION OF THE DRAWING
FIG. 1 is a schematic diagram of an engine with a spark timing computer which is constructed in accordance with the principles of the present invention.
FIG. 1a is a front plan view of a target used in conjunction with the engine and the spark timing computer of FIG. 1.
FIG. 2 is a schematic diagram of the spark timing computer of FIG. 1.
FIG. 3 is a timing diagram for the spark timing computer of FIG. 2 when the engine is below 1200 revolutions per minute.
FIG. 4 is a timing diagram for the spark timing computer of FIG. 2 when the engine is above 1200 revolutions per minute.
DESCRIPTION OF THE PREFERRED EMBODIMENT
The present invention can best be understood by referring to a description of its preferred embodiment shown in FIG. 1. The present invention is used in conjunction with a spark-ignition internal combustion engine 10 having a set of eight spark plugs 11, a distributor 12 and a coil 13. The engine 10 also has a crankshaft 14 on which a flywheel 15 is mounted. Referring briefly to FIG. 1a, the flywheel 15 has reflective surface areas on its face which function as a targer 16. In the preferred embodiment the target 16 has four reflective and four non-reflective surface areas marked on it. Each surface area has a 45° arc and is alternately positioned. The reflective areas are diffusing surfaces in order to spread the reflected light thereby eliminating the necessity for precise optical alignment. For example, a satin-finish aluminum surface functions very well. The target 16 is indexed in such a manner that the reflectance (as seen by a photo-detector) changes at the particular spark timing which is desired during conditions of engine starting. In the preferred embodiment the reflectance was arbitrarily chosen to change from a low value to a high value at this point. During starting conditions the spark occurs at the time the reflectance changes from low to high. This technique ensures that the timing is correct regardless of how erratic or how slow the engine cranks during starting conditions.
An optical source 17, which is generally a galliumarsenide infra-red crystal light-emitting diode which puts out a steady light intensity, is aimed at the target 16 through a lens 18 which focuses the light from the optical source 17 upon the target 16. A photo-detector 19 is aligned with the reflected light from the reflective surface areas of the target 16 and converts the reflected light to an electrical sensor output. An electronic preamplifier 20 amplifies this electrical signal, whose magnitude is proportional to the intensity of the reflected light, in order for the electrical sensor output to be carried through a cable to a computer without interference from external noise sources. A power supply 21 provides electrical power to the electronic preamplifier 20.
The present invention is a spark timing computer 22. It is electrically coupled to the power supply 21 and receives the electrical sensor output from the electronic preamplifier 20. A spark generator 23 is electrically coupled to the spark timing computer 22 and provides a pulse to the coil 13. The spark generator 23 includes a high efficiency ignition coil and a capacitive discharge ignition device which uses a darlington transistor, instead of a silicon controlled rectifier, to discharge the capacitor of the device.
Referring now to FIG. 2, the spark timing computer 22 includes a logic interface 31 which is electrically coupled to the preamplifier 20 from which it receives the sensor signal. The logic interface 31 converts the sensor signal, which has an uncertain amplitude, to a signal suitable to trigger standard-logic integrated circuits. At the same time it processes the sensor signal through circuitry which introduces a noise threshhold and electrical hystereses in order to ensure that any noise present on the signal will not cause false triggering irrespective of the position of the target 16. Otherwise this false triggering could occur if the engine had its ignition on with the target 16 motionless at a troublesome position.
Referring to both FIG. 3 and FIG. 4, the outputs of the preamplifier 20 and logic interface 31 are essentially square waves.
In the spark timing computer 22, a reset logic device 33 receives the square wave from the logic interface 31. The square wave triggers two monostable multivibrators within the reset logic device 33, one of which triggers on the positive-going edge, and is designated start pulse and the other of which triggers on the negative going edge and is designated stop pulse.
The spark timing computer 22 also includes a retard spark control 35 which is electrically coupled to the reset logic device 33 and which lengthens the stop pulse to increase the retard rate and an advance spark control 39 which is electrically coupled to the reset logic device 33 and which lengthens the start pulse to increase the advance rate. The spark timing computer 22 further includes a spark advance inhibit "or" gate 41 which is electrically coupled to the logic interface 31 from which it receives the square wave and to the reset logic device 33 from which it receives a stop pulse. The spark timing computer 22 still further includes a start logic control 43 which is electrically coupled to the reset logic device 33 from which it receives a start pulse. Also included in the spark timing computer 22 is a start or stop logic control 45 which receives both the start pulse and the stop pulse from the reset logic device 33 and sends a reset pulse. An advance initiate control 49 receives a revolutions per minute signal and initiates an advance when the revolutions per minute exceed 1200. A spark advance inhibit control 50 is electrically coupled to the advance initiate control 49 and to the spark advance inhibit "or" gate 41.
Still referring to FIG. 2 the spark timing computer 22 has a non-delayed trigger gate 51 which is electrically coupled to the reset logic device 33 from which it receives a start pulse to provide the ined to the voltage reference 57 and which is also electrically coupled to the start or stop logic control 45 from which it receives the reset pulse. The spark timing computer 22 also has an inhibit gate 61 which is electrically coupled to the output of the integrator 59. The output of both the integrator 59 and the inhibit gate 61 are shown in FIG. 3 for the engine 10 when it is turning less than 1200 revolutions per minute and in FIG. 4 for the engine 10 when it is turning more than 1200 revolutions per minute. The outputs of the integrator 59 and the inhibit gate 61 are designated INTEGRATOR and GATED INTEGRATOR SIGNAL, respectively. It can be seen that the integrator 59 is reset by either the stop pulse or the start pulse.
In the spark timing computer 22 an amplitude peak detector and hold amplifier 63 is electrically coupled to the integrator 59 from which it receives the INTEGRATOR signal shown in FIG. 3 and FIG. 4. The output of the amplitude peak detector and hold amplifier 63 is shown in FIG. 3 and FIG. 4 and is designated as AMPLITUDE PEAK DETECTOR & HOLD AMPLIFIER in both figures. The amplitude peak detector and hold amplifier 63 receives a reset pulse from the start logic control 43 and sends a revolutions per minute signal to the advance initiate control 49. If the engine is turning less than 1200 revolutions per minute, then the advance initiate controls 49 sends a rectangular wave, designated ADVANCE INITIATE CONTROL in FIG. 3 to the spark advance inhibit control 50. If the engine is turning more than 1200 revolutions per minute, then the advance initiate control 49 sends a high signal to the advance inhibit control 50.
Still referring to FIG. 2, the spark timing computer 22 has a voltage scaler 65 which is electrically coupled to the amplitude peak detector and hold amplifier 63 from which it receives the revolutions per minute signal. The voltage scaler 65 is also electrically coupled to a voltage comparator 67 to which it sends a scaled revolutions per minute signal that is designated VOLTAGE SCALER in FIG. 3 and FIG. 4. The voltage comparator 67 is electrically coupled to the inhibit gate 61 from which it receives the GATED INTEGRATOR SIGNAL and also to the non-delayed trigger gate 51 to which it sends an advance pulse thereby closing the non-delayed trigger gate 51. The spark timing computer 22 also has a set of auxiliary advance control amplifiers 69 which are electrically coupled to the amplitude peak detector and hold amplifier 63 and to the voltage scaler 65.
In operation the spark timing computer 22 is best understood by referring first to FIG. 3 which is a series of timing diagrams for the engine 10 when it is turning less than 1200 revolutions per minute and then to FIG. 4 which is a series of timing diagrams for the engine 10 when it is turning more than 1200 revolutions per minute. The output of the photo detector 19 is a square wave which goes positive at 20° before top dead center of a piston (-20) and goes negative at +25°, each cycle running from -20° to +70° is repeated as the crankshaft 14 makes a one-quarter of a revolution. The output of the preamplifier 20 is also a square wave.
The logic interface 31 sends the square wave to the reset logic device 33 which provides both a start pulse at -20° and a stop pulse at +25°. The start or stop logic control 45 provides a reset pulse, which is actually the combination of the start pulse and the stop pulse, and sends it to the integrator 59. The start pulse alone resets the amplitude peak detector and hold amplifier 63. The output of the integrator 59 is a sawtooth wave and the output of the amplitude peak detector and hold amplifier 63 is a series of ramps and level portions which begin at -20° and end at +70° of each cycle.
When the engine 10 is turning less than 1200 revolutions per minute the advance initiate control 49 sends a rectangular wave in phase with the output of the logic interface 31 to the spark advance inhibit control 50 thereby activating the spark advance inhibit control 50 and closing the inhibit gate 61 so that there is no GATED INTEGRATOR SIGNAL being sent to the voltage comparator 67. Since there is no GATED INTEGRATOR SIGNAL sent to the voltage comparator 67, it does not send an advance pulse to the non-delayed trigger 51 thereby leaving this gate open so that the start pulse serves as the initial timing trigger to the non-delayed trigger gate 51 and triggers the high voltage trigger multivibrator 55 through the high voltage trigger "or" gate 53. The high voltage trigger monostable multivibrator 55 sends its output through a buffer amplifier 56 and the output of the buffer amplifier 56 is the spark trigger that is transmitted to the spark generator 23. The spark trigger occurs at 20° before top dead center of a piston for all engine speeds below 1200 revolutions per minute.
When the engine 10 is turning more than 1200 revolutions per minute the advance control 49 sends a high signal to the spark advance inhibit control 50 which has an output that is in phase with the square wave output of the logic interface 31. The inhibit gate 61 closes whenever the output of the spark advance inhibit control 50 is high and opens whenever the same output is low and operates in conjunction with the output of the integrator 59 to provide a GATED INTEGRATOR SIGNAL. The INTREGRATOR signal is inhibited during the prefire interval in order to prevent false triggering. The amplitude of the INTEGRATOR signal is determined by the rotational speed of the engine's 10 crankshaft 14 and varies linearly therewith. The voltage scaler 65 scales the AMPLITUDE PEAK DETECTOR & HOLD AMPLIFIER signal in half to provide a VOLTAGE SCALER signal and sends this signal to the voltage comparator 67 in which it is compared to the GATED INTEGRATOR SIGNAL. When the GATED INTEGRATOR SIGNAL exceeds the VOLTAGE SCALER signal it closes the non-delayed trigger gate 51 and triggers the high voltage trigger monostable multivibrator 55 through the high voltage trigger "or" gate 53. When the engine 10 is turning more than 1200 revolutions per minute the advance is initially set at 421/2° before top dead center of a piston (-421/2°). From the 421/2° advance the spark timing computer 22 alters the advance in the following manner. The revolutions per minute signal, RPMS, from the amplitude peak detector and hold amplifier 63 is sent to the voltage scaler 65 which scales the RPMS in half as can be readily seen in FIG. 4 where the output of the voltage scaler 65 is designated VOLTAGE SCALER. The VOLTAGE SCALER signal and the GATED INTEGRATOR SIGNAL are compared in the voltage comparator 67 which sends a signal whenever the GATED INTEGRATOR SIGNAL exceeds the VOLTAGE SCALER signal to the non-delayed trigger gate 51 and the high voltage trigger "or" gate 53. Since the VOLTAGE SCALER signal is one half the peak amplitude of the GATED INTEGRATOR SIGNAL, it takes the GATED INTEGRATOR SIGNAL only one half of the 45° rotation to reach the amplitude level of the VOLTAGE SCALER signal, i.e. 221/2°. Therefore, the advance is now (221/2° + 20°) = 421/2°.
The auxiliary advance control amplifiers 69 operate in the spark timing computer 22 by changing the scaling factor within the voltage scaler 65. The auxiliary advance control amplifiers 69 provide the spark timing computer 22 with the capability of not only varying the advance or retard characteristic in a continuous variation, but also introducing steps in the variation of the advance or retard characteristic. The advance can also be varied by lengthening the STOP PULSE or the START PULSE. Lengthening the STOP PULSE will cause the integrator 59 to start later thereby retarding the spark. This effect is more pronounced as the engine turns faster because the integrator 59 starts later in its timing cycle as the engine 10 speeds up. Lengthening the START PULSE will prevent the RPMS from reaching its normal level and allow the coincidence between the GATED INTEGRATOR SIGNAL and the VOLTAGE SCALER signal to occur sooner thereby advancing the spark timing. Therefore the spark timing computer 22 can either increase or decrease spark timing in relation to the revolutions per minute signal.
The present invention requires only a reference angle detecting device, because it uses an analog computer which, unlike a digital computer, is able to derive the revolutions per minute information from the reference angle as it varies with time. Furthermore, although it is an analog computer, its design is such that is also provides stability against variations in both voltages from the power supply and the ambient temperature.
The primary advantage of the spark timing computer is that its use improves the performance of an engine. It is not only a reliable computer for spark timing, but also a versatile computer. The spark timing computer may be used with any reference angle detecting devices such as optical source/photo-detector arrangements as in the preferred embodiment, mechanical devices, magnetic devices, and electrical devices. Furthermore, the voltage scaler and reset pulses may be set for any particular advance or retard characteristic desired.
From the foregoing it can be seen that a spark timing computer has been described for use in controlling the ignition timing of a spark-ignition internal combustion engine.
It should be noted that the schematic drawing of the system for advancing or retarding the spark timing is not drawn to scale and that distances of and between the figures are not to be considered significant. | The invention is a spark timing computer which includes a resetting device for forming a start pulse and a stop pulse which is electrically coupled to the reference angle detecting device, an integrator which is electrically coupled to a reference voltage which is reset by either a stop pulse or a start pulse from the resetting device, a peak detecting device for detecting and holding the peak amplitude of the integrator and being reset by a start pulse from the resetting device, a scaling device for scaling the peak amplitude of the peak detecting device which is electrically coupled to the peak detecting device, a comparing device for comparing the scaled peak amplitude of the peak detecting device with the output signal of the integrator and a triggering device for forming a spark trigger in response to a signal from the comparing device and for sending the spark trigger to a spark generator. The spark timing computer also includes devices for varying the stop pulse width and the start pulse width which are electrically coupled to the resetting device. The spark timing computer further includes a triggering device for providing a spark trigger in response to the start pulse of the resetting device and an inhibiting device for inhibiting the triggering device in response to a signal from the peak amplitude detecting device indicating a particular rotational speed of the engine. | 5 |
CROSS-REFERENCE TO RELATED APPLICATIONS
This application claims priority benefits to Chinese Patent Application No. 200810105513.3 filed on Apr. 29, 2008, the contents of which are incorporated herein by reference.
BACKGROUND OF THE INVENTION
1. Field of the Invention
The invention relates to a health-promoting composition, and more particularly to a health promoting composition comprising selenium-rich yeast and yeast beta-glucan.
2. Description of the Related Art
Although it is toxic in large doses, selenium is an essential micronutrient for animals. Dietary selenium comes from nuts, cereals, meat, fish, and eggs. Brazil nuts are the richest ordinary dietary source (though this is soil-dependent, since the Brazil nut does not require high levels of the element for its own needs). High levels are found in kidney, tuna, crab, and lobster, in that order. In general, however, the content of selenium in human diet is limited and insufficient.
In humans, selenium is a trace element nutrient which functions as cofactor for reduction of antioxidant enzymes such as glutathione peroxidases and certain forms of thioredoxin reductase found in animals and some plants (this enzyme occurs in all living organisms, but not all forms of it in plants require selenium).
Glutathione peroxidase (GSH-Px) catalyzes certain reactions which remove reactive oxygen species such as peroxide:
2GSH+H 2 O 2 -GSH-Px→GSSG+2H 2 O
Selenium also plays a role in the functioning of the thyroid gland by participating as a cofactor for the three known thyroid hormone deiodinases.
Selenium is a component of the unusual amino acids selenocysteine, and selenomethionine, and the amino acid dimer selenocystine, and as such is an important building block of the human body.
Furthermore, selenium is an important component in enzymes affecting metabolism, reproduction, immune system as well as the well being of human beings. It is also known to play a role in preventing cancer, anti-oxidation, and anti-aging.
Since there is insufficient amount of selenium present in normal diet, it is advantageous to supply selenium as food supplement. Inorganic selenium in the form of selenite, or organic selenium, for example, in the form of selenium-rich yeast may be supplied. However, there is a remarkable difference between inorganic selenium and organic selenium in terms of absorption and toxicity, i.e., inorganic selenium is much harder to absorb and has a much higher toxicity. Therefore, a commonly-used source of organic selenium is selenium-enriched yeast.
Using modern biotechnology, selenium-enriched yeast can be made by converting inorganic selenium into organic selenium using brewer's yeast and then separating and refining the organic selenium. 99% or more of all selenium in selenium-enriched yeast is in form of organic selenium, which facilitates faster absorption and low toxicity.
Yeast beta-glucan is a water-insoluble polysaccharide having β-1, 3-D-glucan as main chains and β-1, 6-D-glucan as side chains. It is an important component of yeast cell wall. It can improve immunity, prevent cancer, inhibit bacteria and reinforce resistance against illnesses.
In recent years, there have been many studies on selenium, majority of them focusing on the nutritional mechanism, and a large amount of products have appeared. However, there have been few products made from organic selenium or selenium-rich yeast. Specifically, rather than taking the comprehensive nutritional factor is into account, products have appeared with the sole goal of supplying selenium. In addition, researchers on yeast beta-glucan mainly concentrate on extraction and purification of beta-glucan, and few products, if any, exist.
SUMMARY OF THE INVENTION
Therefore, it is one objective of the invention to provide a composition comprising selenium-rich yeast and yeast beta-glucan exhibiting anti-oxidative, anti-aging, cancer preventive and immune-enhancing properties.
To achieve the above objectives, in accordance with one embodiment of the invention, provided is a nutritional composition comprising by weight: between 0.05 and 30% organic selenium-enriched yeast; between 1 and 90% purified yeast beta-glucan; between 0.5 and 60% Vitamin C; and between 0.5 and 40% Vitamin E.
In certain classes of this embodiment, the composition comprises by weight: between 0.5 and 10% selenium-enriched yeast; between 20 and 58% yeast beta-glucan; between 20 and 40% Vitamin C; and between 20 and 30% Vitamin E.
In certain classes of this embodiment, the selenium-enriched yeast comprises between 500 and 2000 ppm of selenium.
In certain classes of this embodiment, the yeast beta-glucan comprises by weight between 20 and 90% of beta-glucan.
In certain classes of this embodiment, the composition further comprises by weight: between 0 and 1% Vitamin A; between 0 and 5% β-carotene; between 0 and 1% Vitamin B 1 ; between 0 and 1% Vitamin B 2 ; between 0 and 1% Vitamin B 6 ; between 0 and 5% lycopene; between 0 and 20% grape seed extract; between 0 and 20% α-lipoic acid; between 0 and 20% propolis; between 0 and 10% ginkgo biloba extract; between 0 and 10% ginseng extract; between 0 and 30% calcium carbonate; between 0 and 30% calcium gluconate; between 0 and 30% calcium lactate; between 0 and 10% zinc gluconate; between 0 and 10% zinc lactate; between 0 and 10% ferrous gluconate fumarate; between 0 and 1% ferrous lactate; and between 0 and 10% ferrous fumarate.
The composition according of the invention can be formulated in the form of granules, powder, capsules, tablets, or liquid by adding auxiliary materials. The auxiliary materials are without limitation starch, milk powder, dextrin, microcrystalline cellulose, hydroxypropyl sodium cellulose, sugar, food flavoring, and so on.
Advantages of the Invention Include
1) the invention employs safe and highly-effective organic selenium-enriched yeast as the main selenium source, and the selenium content in the composition is between 10 and 1000 μg/g, which ensures its safety and health effects; and
2) high-purity yeast beta-glucan and natural Vitamin C and E are included in the composition to facilitate the synergistic effect, and to obtain a composition enriched in organic selenium and yeast beta-glucan promoting enhanced immunity and resistance to illness.
DETAILED DESCRIPTION OF THE EMBODIMENTS
Definitions:
The term “selenium-enriched yeast,” as used herein, refers to dried, pulverized cells of Saccharomyces cerevisiae which have incorporated selenium into organic compounds. Selenium-enriched yeast used herein was purchased from Angel Yeast Co., Ltd. (Add: 24 Zhongnan Rd. Yichang Hubei 443003, China, Tel: 0086-717-6369254) under the commercial name of Selenium-enriched Yeast (selenium content of 2000 ppm). Selenium-enriched yeast used herein was prepared as follows: yeast ( Saccharomyces cerevisiae ) was cultured in a culture medium with enriched sodium selenite, subsequently the yeast was harvested, centrifugated and dried.
The term “yeast beta-glucan,” as used herein, refers to polysaccharide chains of D-glucose molecules, with the six-sided D-glucose rings connected at the 1 and 3 positions, wherein side chains 1, 6-glucan side-chains branch off from the longer beta-1, 3 glucan backbone, produced by yeast. Yeast beta-glucan used herein was purchased from Angel Yeast Co., Ltd. (Add: 24 Zhongnan Rd. Yichang Hubei 443003, China, Tel: 0086-717-6369254) under the commercial name of 80% Yeast Glucan. Yeast beta-glucan used herein was prepared as follows: yeast was autolysed and centrifugated, and then yeast cell wall was collected, from which yeast glucan was extracted using base and acid.
Vitamin C was purchased from CSPC Weisheng Pharmaceutical (Shijiazhuang) Co., Ltd. (Add: No. 236 Yellow Rd., Shijiazhuang New-high Technology Industry Development Zone, Hebei, China, Tel: 0086-311-85388577) under the commercial name of 99% Coated Ascorbic Acid.
Vitamin E was purchased from BASF Vitamin Co., Ltd. (Add: No. 88 Yunhai Rd., Shenyang Economy and Technology Development Zone, Shenyang, China, Tel: 0086-24-25360235) under the commercial name of 50% Vitamin E.
β-carotene was purchased from BASF Vitamin Co., Ltd. (Add: No. 88 Yunhai Rd., Shenyang Economy and Technology Development Zone, Shenyang, China, Tel: 0086-24-25360235) under the commercial name of 10% β-carotene.
Vitamin B 1 was purchased from Guangzhou Topvita Food Ingredients Co., Ltd. (Tel: 0086-20-38390003) under the commercial name of 99% Thiamine hydrochloride.
Vitamin B 2 was purchased from Guangzhou Topvita Food Ingredients Co., Ltd. (Tel: 0086-20-38390003) under the commercial name of 99% Riboflavin.
Vitamin B 6 was purchased from Guangzhou Topvita Food Ingredients Co., Ltd. (Tel: 0086-20-38390003) under the commercial name of 99% Pyriddoxine.
Lycopene was purchased from Guangzhou Topvita Food Ingredients Co., Ltd. (Tel: 0086-20-38390003) under the commercial name of 6% Lycopene.
The term “grape seed extract,” as used herein, refers to industrial derivatives from whole grape seeds comprising polyphenols, including oligomeric proanthocyanidins recognized as antioxidants. The grape seed extracts used herein was purchased from Ningbo Osaki Biotech Co., Ltd. (Add: No. 521 Yuanbaoshan Rd. Beilun Ningbo China, Tel: 0086-574-86119676) under the commercial name of Grape Seed Extract, with 95% Proanthocyanidins.
α-Lipoic acid was purchased from Tianjin Tiancheng Pharmaceutical Co., Ltd. (Add: P.O. BOX 4005 North Sanjing Rd. Yangliuqing Xiqing District, Tianjin, China, Tel: 0086-22-27390520) under the commercial name of 99% α-Lipoic acid.
The term “propolis,” as used herein, refers to a resinous mixture that bees collect from tree buds, sap flows, or other botanical sources. Propolis used herein was purchased from Henan Purui Bees Products Co., Ltd. (Add: Dazhou Industrial zone, Changge, Henan, 461507, China, Tel: 0086-374-6865389) under the commercial name of 30-90% Propolis Powder.
The term “ginkgo biloba extract,” as used herein, refers to an extract from Gingko biloba, a unique species of tree cultivated in China, Korea, and parts of Japan with no close living relatives, comprising flavonoid glycosides and terpenoids (ginkgolides, bilobalides). The ginkgo biloba extract used herein was purchased from Ningbo Osaki Biotech Co., Ltd. (Add: No. 521 YuanBaoshan Rd. Beilun Ningbo China, Tel: 0086-574-86119676) under the commercial name of Ginkgo Biloba Leaf Extract, with total Ginkgo flavone glycoside more than 24%.
The term “ginseng extract,” as used herein, refers to an extract from Panax ginseng (white ginseng). The ginseng extract used herein was purchased from Ningbo Osaki Biotech Co., Ltd. (Add: No. 521 YuanBaoshan Rd. Beilun Ningbo China. Tel: 0086-574-86119676) under the commercial name of Panax Ginseng Root Extract, with 20% Ginsenosides.
Calcium carbonate was purchased from ZhengZhou RuiPu Biology Engineering Co., Ltd. (Add: No. 96 Ruida Rd. Hi-Tech Industries Development Zone ZhengZhou China. Tel: 0086-371-67896828) under the commercial name of Calcium carbonate with concentration no less than 96%.
Calcium gluconate was purchased from ZhengZhou RuiPu Biology Engineering Co., Ltd. (Add: No. 96 Ruida Rd. Hi-Tech Industries Development Zone ZhengZhou China. Tel: 0086-371-67896828) under the commercial name of Calcium gluconate with concentration no less than 99%.
Calcium lactate was purchased from ZhengZhou RuiPu Biology Engineering Co., Ltd. (Add: No. 96 Ruida Rd. Hi-Tech Industries Development Zone ZhengZhou China. Tel: 0086-371-67896828) under the commercial name of Calcium lactate with concentration no less than 98%.
Zinc gluconate was purchased from ZhengZhou RuiPu Biology Engineering Co., Ltd. (Add: No. 96 Ruida Rd. Hi-Tech Industries Development Zone ZhengZhou China. Tel: 0086-371-67896828) under the commercial name of Zinc gluconate with concentration no less than 97%.
Zinc lactate was purchased from ZhengZhou RuiPu Biology Engineering Co., Ltd. (Add: No. 96 Ruida Rd. Hi-Tech Industries Development Zone ZhengZhou China. Tel: 0086-371-67896828) under the commercial name of Zinc lactate with concentration no less than 98%.
Ferrous gluconate fumarate was purchased from ZhengZhou RuiPu Biology Engineering Co., Ltd. (Add: No. 96 Ruida Rd. Hi-Tech Industries Development Zone, ZhengZhou, China. Tel: 0086-371-67896828) under the commercial name of Ferrous gluconate with concentration no less than 95%.
Ferrous lactate was purchased from ZhengZhou RuiPu Biology Engineering Co., Ltd. (Add: No. 96 Ruida Rd. Hi-Tech Industries Development Zone, ZhengZhou, China. Tel: 0086-371-67896828) under the commercial name of Ferrous lactate with concentration no less than 98%.
Ferrous fumarate was purchased from ZhengZhou RuiPu Biology Engineering Co., Ltd. (Add: No. 96 Ruida Rd. Hi-Tech Industries Development Zone, ZhengZhou China. Tel: 0086-371-67896828) under the commercial name of Ferrous fumarate with concentration no less than 93%.
The following embodiments are solely intended to describe the invention, not to limit the scope of the invention.
EXAMPLE 1
The nutritional composition of this example comprises by weight: 10% selenium-enriched yeast (selenium content of 2000 ppm), 30% yeast beta-glucan (beta-glucan content of 80% by weight), 20% Vitamin E, and 40% Vitamin C.
The preparation process comprises the following steps:
a) grinding: grinding Vitamin C and Vitamin E with a superfine pulverizer before mixing; b) sieving: passing the grinded Vitamin C and Vitamin E through a 60 mesh sieve, and passing the selenium-enriched yeast and the yeast beta-glucan through a 60 mesh sieve; c) mixing: manually mixing sieved selenium-enriched yeast with Vitamin E; placing the mixture into a mixer; placing the sieved beta-glucan and the grinded Vitamin C into V-shaped mixer to mix for 45 minutes. The mixer can be any type of mixer known in the art; d) formulating: formulating the mixture into capsules, 1 g material for each capsule; e) packing: packing 200 capsules into a bottle.
To ensure safety of products, all of the above steps are completed in a GMP facility.
EXAMPLE 2
The preparation process is substantially the same as that in example 1, with the only difference being that the nutritional composition comprises by weight: 30% selenium-enriched yeast (selenium content of 1000 ppm), 69% yeast beta-glucan (beta-glucan content of 70%), 0.5% Vitamin E, and 0.5% Vitamin C.
EXAMPLE 3
The preparation process is substantially the same as that in example 1, with the only difference being that the nutritional composition comprises by weight: 0.05% selenium-enriched yeast (selenium content of 500 ppm), 90% yeast beta-glucan (beta-glucan content of 90%), 6.95% Vitamin E, and 3% Vitamin C.
EXAMPLE 4
The nutritional composition of this example comprises by weight: 5% selenium-enriched yeast (selenium content of 1000 ppm), 30% yeast beta-glucan (beta-glucan content of 80%), 20% Vitamin E, 30% Vitamin C, and 15% sucrose.
The preparation process comprises the following steps:
a) grinding: grinding sucrose, Vitamin C and Vitamin E with a superfine pulverizer before mixing; b) sieving: passing the grinded sucrose, Vitamin C and Vitamin E through a 60 mesh sieve, and passing the selenium-enriched yeast and the yeast beta-glucan through a 60 mesh sieve; c) mixing: mixing sieved sucrose, Vitamin C, Vitamin E, selenium-enriched yeast, and yeast beta-glucan with sterile water in the proportion of 1:10 (n/v, g/mL) to form a liquid for oral administration; d) packing: canning the oral liquid into bottles, 100 mL to each bottle.
To ensure safety of products, all of the above steps are completed in a GMP facility.
EXAMPLE 5
The nutritional composition of this example comprises by weight: 10% selenium-enriched yeast (selenium content of 1500 ppm), 40% yeast beta-glucan (beta-glucan content of 90%), 10% Vitamin E, 10% Vitamin C, 5% β-carotene, 5% lycopene, 5% propolis, 5% starch, and 10% sucrose.
The preparation process comprises the following steps:
a) grinding: grinding Vitamin C and Vitamin E with a superfine pulverizer before mixing; b) sieving: passing the grinded Vitamin C and Vitamin E through a 60 mesh sieve, and passing the selenium-enriched yeast and the yeast beta-glucan through a 60 mesh sieve; c) mixing: manually mixing sieved selenium-enriched yeast with Vitamin E; placing the mixture into a V-shaped; adding sieved beta-glucan and grinded Vitamin C and mixing for 45 minutes; d) formulating: formulating the mixed materials into tablets, each tablet being 1.0 g; and e) packing: packing into bottles or aluminum foil.
To ensure safety of products, all of the above steps are completed in a GMP facility.
EXAMPLE 6
The nutritional composition of this example comprises by weight: 17% selenium-enriched yeast (selenium content of 2000 ppm), 30% yeast beta-glucan (beta-glucan content of 80%), 10% calcium carbonate, 10% propolis, 5% Vitamin E, 5% β-carotene, 5% ginkgo biloba extract, 5% grape seed extract, 5% Vitamin C, 0.5% Vitamin B 1 , 0.5% Vitamin B 2 , 0.5% Vitamin B 6 , 1% ferrous lactate, and 0.5% zinc gluconate.
The preparation process comprises the following steps:
a) grinding: grinding Vitamin C and Vitamin E in a superfine pulverizer before mixing; b) sieving: passing the grinded Vitamin C and Vitamin E through a 60 mesh sieve, and passing the selenium-enriched yeast and the yeast beta-glucan through a 60 mesh sieve; c) mixing: manually mixing sieved selenium-enriched yeast with Vitamin E, placing in a V-shaped mixer; adding sieved yeast beta-glucan and grinded Vitamin C into the mixer and mixing for 45 minutes; d) formulating: placing the mixture into capsules, 1 g material for each capsule; e) packing: packing capsules into bottles, 100 capsules per bottle.
To ensure safety of products, all of the above steps are completed in a GMP facility.
EXAMPLE 7
The preparation process is substantially the same as that in example 6, with the only difference being that the nutritional composition comprises by weight: 0.5% selenium-enriched yeast (selenium content of 1000 ppm), 58% yeast beta-glucan (beta-glucan content of 90%), 4.5% Vitamin E, 20% Vitamin C, 1% Vitamin A, 5% α-lipoic acid, 4% ginseng extract, 2% calcium carbonate, 1% zinc lactate, and 4% ferrous gluconate.
EXAMPLE 8
The preparation process is substantially the same as that in example 6, with the only difference being that the nutritional composition comprises by weight: 1% selenium enriched yeast (selenium content of 1500 ppm), 20% yeast beta-glucan (beta-glucan content of 60%), 30% Vitamin E, 15% Vitamin C, 0.5% Vitamin A, 1% Vitamin B 1 , 1% Vitamin B 2 , 1% Vitamin B 6 , 20% grape seed extract, 2% calcium lactate, 2.5% ferrous fumarate, and 5% dextrin.
EXAMPLE 9
Immunity Experiment on Composition
60 male BALB/c mice of clean grade with body weight 18-22 g were purchased from Shanghai Xipu'er-Bikai Experimental Animal Co., Ltd. (Add: No. 779 Laohumin Rd., Shanghai 200237, China, Tel: 0086-21-64776624) and randomly assigned into an experimental group, four control groups and a blank group with 10 animals in each group.
0.50 g/kg·bw of the nutritional composition of the Example 1 were administered to the experimental group by gavage daily. 0.05 g/kg·bw of selenium-enriched yeast (control group 1), 0.15 g/kg·bw of yeast beta-glucan (control group 2), 0.20 g/kg·bw of Vitamin C (control group 3) and 0.10 g/kg·bw of Vitamin E (control group 4) were administered to the four control groups respectively. Physiological saline was administered to the blank group.
Three months later, a plurality of immune index of mice comprising thymus weight/body weight ratio, humoral immunity function (antibody index) and cellular immune function (NK cell activity) were measured. The measurement method was the same as the method for evaluating health food.
Antibody cell
detection
Thymus
Quantity of
weight/body
plaque forming
NK cell
Animal
weight ratio
cells (/106
activity
Groups
quantity
(mg/g)
spleen cells)
(%)
Blank group
10
1.83 ± 0.44
93 ± 30
17.69 ± 5.62
Control group 1
10
1.73 ± 0.25
92 ± 27
14.89 ± 7.92
Control group 2
10
1.84 ± 0.61
92 ± 34
17.62 ± 9.91
Control group 3
10
1.80 ± 0.57
87 ± 41
18.18 ± 4.14
Control group 4
10
1.90 ± 0.33
96 ± 21
18.02 ± 5.31
Experimental
10
2.87 ± 0.48*
184 ± 41**
32.99 ± 10.08**
group
Remark:
Symbol “*” represents p < 0.05 by comparison with the blank group;
symbol “**” represents p < 0.01 by comparison with the blank group.
From the experimental results, a conclusion can be drawn that compared with the blank group and four control groups, the nutritional composition of the Example 1 can enhance the immunity and improve the antibody producing capacity and NK cell activity of the mice significantly; each control group (administered by an ingredient of the nutritional composition of the Example 1) has no significant influence on the immunity of the mice; the nutritional composition of the Example 1 has enhanced the immunity of the mice by comparison with the four control groups.
EXAMPLE 10
Anti-Oxidation Experiment on Composition
297 healthy male and female volunteers between 45 and 65 years of age were selected and randomly assigned into an experimental group, four control groups and a blank group. During the experiment, all the volunteers kept original living and dietary habits.
500 mg of the nutritional composition of the Example 2 were administered to the experimental group each time, two times a day for three consecutive months. 150 mg of selenium-enriched yeast (control group 1), 450 mg of yeast beta-glucan (control group 2), 2.5 mg of Vitamin C (control group 3) and 2.5 mg of Vitamin E (control group 4) were administered to the four control groups respectively each time, two times a day for three consecutive months. Subsequently, the content of lipid peroxide (malondialdehyde (MDA)), superoxide dismutase (SOD) activity and glutathione peroxidase (GSH-PX) activity of the volunteers were measured. The measurement method was the same as the method for evaluating health food.
From the experimental results, a conclusion can be drawn that the nutritional composition of the Example 2, on the one hand, can enhance the anti-oxidation capacity for human body and improve SOD activity and GSH-PX activity, and on the other hand, can decrease the MDA content in humans significantly. Each control group has no significant influence on the anti-oxidation capacity for human body. The nutritional composition of the Example 2 has enhanced the anti-oxidation capacity for human body by comparison with the four control groups.
Blank group
Experimental group
Control group 1
Volunteer quantity
50
51
45
Age
51.3 ± 6.7
52.1 ± 7.3
50.1 ± 5.8
Male/Female
25/25
28/23
25/20
MDA
Before
5.74 ± 0.50
5.72 ± 0.55
5.69 ± 0.40
content
administration
(nmol/mL)
After
5.66 ± 0.41
4.76 ± 0.60#*
5.70 ± 0.65
administration
SOD
Before
13330.4 ± 2091.2
13205.8 ± 1267.6
13298.7 ± 1497.4
activity
administration
(U/gHb)
After
13264.9 ± 1767.1
14350.9 ± 1429.2#*
13378.1 ± 1783.6
administration
GSH-Px
Before
121.9 ± 12.13
122.2 ± 11.77
120.4 ± 11.23
activity
administration
(U/mL)
After
120.1 ± 11.83
128.1 ± 11.20#*
122.5 ± 15.44
administration
Control group 2
Control group 3
Control group 4
Volunteer quantity
47
51
53
Age
53.6 ± 8.1
49.4 ± 7.8
50.5 ± 6.2
Male/Female
22/25
26/25
25/28
MDA
Before
5.61 ± 0.51
5.77 ± 0.65
5.74 ± 0.55
content
administration
(nmol/mL)
After
5.60 ± 0.34
5.75 ± 0.60
5.72 ± 0.65
administration
SOD
Before
13278.5 ± 1879.4
13335.1 ± 1466.6
13297.0 ± 2193.7
activity
administration
(U/gHb)
After
13287.3 ± 1997.7
13345.5 ± 1472.7
13375.6 ± 2014.7
administration
GSH-Px
Before
117.5 ± 15.22
121.6 ± 15.67
120.8 ± 13.12
activity
administration
(U/mL)
After
118.8 ± 14.73
123.7 ± 15.33
121.9 ± 9.78
administration
Remark:
Symbol “#” represents p < 0.01 by self-comparison;
symbol “*” represents p < 0.01 by comparison between groups.
While particular embodiments of the invention have been shown and described, it will be obvious to those skilled in the art that changes and modifications may be made without departing from the invention in its broader aspects, and therefore, the aim in the appended claims is to cover all such changes and modifications as fall within the true spirit and scope of the invention. | A nutritional composition comprising by weight: between 0.05 and 30% selenium-enriched yeast; between 1 and 90% yeast beta-glucan; between 0.5 and 60% Vitamin C; and between 0.5 and 40% Vitamin E. The composition features anti-oxidative, anti-aging, cancer-preventing, and immune-stimulating properties. | 0 |
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